WO1998001104A1 - Cosmetic preparations containing fluorinated oils - Google Patents

Cosmetic preparations containing fluorinated oils Download PDF

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Publication number
WO1998001104A1
WO1998001104A1 PCT/JP1997/002343 JP9702343W WO9801104A1 WO 1998001104 A1 WO1998001104 A1 WO 1998001104A1 JP 9702343 W JP9702343 W JP 9702343W WO 9801104 A1 WO9801104 A1 WO 9801104A1
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WO
WIPO (PCT)
Prior art keywords
oil
fluorinated
weight
fluorine
aliphatic group
Prior art date
Application number
PCT/JP1997/002343
Other languages
French (fr)
Japanese (ja)
Inventor
Masamichi Morita
Eiji Seki
Motonobu Kubo
Original Assignee
Daikin Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Priority to JP50505698A priority Critical patent/JP3622204B2/en
Priority to EP97929542A priority patent/EP0938885A4/en
Priority to US09/214,153 priority patent/US6136331A/en
Publication of WO1998001104A1 publication Critical patent/WO1998001104A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/69—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing fluorine
    • A61K8/70—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing fluorine containing perfluoro groups, e.g. perfluoroethers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
    • A61Q1/06—Lipsticks
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/12—Face or body powders for grooming, adorning or absorbing
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair

Definitions

  • the present invention relates to a cosmetic containing a fluorinated oil.
  • the present invention relates to a fluorine-containing compound which is not compatible with a hydrocarbon-based oil when used in combination with a hydrocarbon-based oil, and which does not inhibit the oil repellency of the fluorine-compound-treated powder when used in combination with a fluorine-compound-treated powder.
  • the present invention relates to a cosmetic containing a system oil. This fluorinated oil has the characteristics of high safety and affinity for the skin, and inexpensiveness, in addition to the above characteristics.
  • perfluoropolyether is incompatible with hydrocarbon oils when used in combination with hydrocarbon oils (lipophobic), and when used in combination with fluorine compound treated powders, It does not impair the oil repellency of
  • perfluoropolyether is a compound originally developed as a lubricant for vacuum pumps and the like, and is not necessarily optimal for blending into cosmetics.
  • perfluoropolyether has a poor affinity for the skin and is very expensive because the hydrogen of the polyether is completely replaced by fluorine.
  • An object of the present invention is to provide a fluorine-based oil which does not impair the oil repellency of the powder treated with a fluorine compound when used in combination with the powder treated with a fluorine compound, has good affinity for the skin, and is inexpensive.
  • a specific fluorinated oil has an oil-oleophobicity equivalent to that of perfluoropolyether, and a repellency of fluorinated compound-treated powder. It does not impair oiliness. 3 It is safe against skin, and because it is not completely fluorinated, it has a higher affinity for skin than perfluoropolyether. I found what I could do.
  • the present invention is to provide a fluorine-based oil which does not impair the oil repellency of the powder treated with a fluorine compound when used in combination with the powder treated with a fluorine compound, has good affinity for the skin, and is inexpensive.
  • R 1 'and R represent a hydrogen atom or a partially or completely fluorinated aliphatic group having a prime number of 1 to 20, R lb and ⁇ ⁇ ⁇ , a hydrogen atom, a carbon number
  • a cosmetic comprising 0.01 to 100% by weight of a fluorine-based oil (I) represented by the formula:
  • R z ′ is a hydrogen atom, a partially or completely fluorinated aliphatic group having 1 to 20 carbon atoms
  • R 2b , a shaku 2 ⁇ 1 3 ⁇ 4 3 ⁇ 4 is a coal number 1 to 20 aliphatic groups, partially or fully fluorinated C 1-20 aliphatic groups It is.
  • at least one of R 2 "to R 2d is a partially or completely fluorinated aliphatic group having a carbon number of 1 to 20.
  • M is Ru number der 1-20.
  • a cosmetic comprising 0.01 to 100% of a fluorine-based oil (II) represented by the formula:
  • X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a partially or fully fluorinated aliphatic group having 1 to 30 carbon atoms
  • Y is a partially or completely fluorinated group.
  • a cosmetic comprising 0.01 to 100% by weight of a fluorinated oil (III) represented by the formula:
  • the present invention provides 1 to 30% by weight of at least one selected from the group consisting of the fluorinated oils (1), (II) and (II ⁇ ) and 5 to 95% by weight of a fluorine compound-treated powder.
  • % Cosmetics are provided.
  • a fluorinated oil (1), a fluorinated oil (II) and Z or a fluorinated oil (III) are used.
  • R '', R lb , R, R ld , R 2 ⁇ R 2 ⁇ R z ⁇ R 2d , X and Y are partially or completely When it is a fluorinated aliphatic group, it may have an oxygen atom or an unsaturated bond.
  • a partially fluorinated aliphatic group is, for example, R] D OCH 2 group, etc.
  • R 1D is a partially or fully fluorinated aliphatic group (eg, an alkyl group)). Examples of partially or fully fluorinated aliphatic groups include:
  • R ' have ⁇ R, R 2b, and R2o, when Ru der aliphatic group having 1 to 20 carbon atoms and may have an oxygen atom.
  • the aliphatic group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, hydroxymethyl, and 2-hydroxyxethyl ( And a hydroxyalkyl group such as CH 2 CH 2 OH).
  • R lb , R, R 2b and R 2t in the repeating unit may be the same or different.
  • R 1 ′ to R ld , R 2 ′ to R 2 d , ⁇ , and ⁇ the preferred number of carbon atoms is 1
  • fluorinated oil (I) examples include the following.
  • each of R a and R c is the same or different, and one CF 2 CF 2 H,
  • Fluorinated oils (II) include the following,
  • fluorinated oil (III) examples include the following, C 3 F 7 OC (CF 3 ) FCF 20 (CH 2 CF 2 CF 20 ) n CH 2 CF 2 C0 2 CH 3
  • Fluorinated oil (I) can be synthesized by various methods.
  • a fluorine-based oil (I) can be synthesized by reacting a raw material alcohol compound with fluorofluorin.
  • the alcohol compound as a raw material include various compounds such as glycerin, diglycerin, polyglycerin, and compounds generally called hindered alcohols and hindered alcohol oligomers, which limit the present invention. Not a thing.
  • a solvent for the reaction between the starting alcohol and fluorofluorin As the solvent, a non-protonic polar solvent can be used.
  • the solvent examples include DMF (dimethylformamide), DMSO (dimethyl sulfokind), NMP (N-methylpyrrolidone), sulfolane, diglyme, and triglyme. , Ether, THF, chloroform, dichloromethane, methyl ethyl ketone, acetone, etc. Water may be added to the reaction solution.
  • a reaction catalyst or HF is produced as a byproduct, a base is used as a scavenger.
  • a neutral catalyst may be used.
  • the basic catalyst is KOH, N aOH.
  • K 2 C0 3, Na 2 C0 3, N aHC0 such third inorganic bases, Toriwechiruamin, and organic bases such as Toripuchiruamin.
  • the reaction temperature is preferably from 10 to 200 ° C, preferably from 0 to 150 ° C, particularly preferably from 10 to 120 ° C.
  • the reaction pressure is not particularly limited, but is preferably from 0 to 20 kgZcm 2 G (gauge pressure), particularly preferably. Is 0 to; I 0 kgZcm 2 G.
  • the reaction time is 0.5 to 100 hours, preferably 2 to 50 hours.
  • Fluorinated oil (II) can be synthesized by various methods.
  • a fluorine-based oil (II) can be synthesized by reacting an alcohol compound as a raw material with a fluororefin.
  • an alcohol compound as a raw material there are various examples of the alcohol compound as a raw material, and compounds generally referred to as hindered alcohols and hindered alcohol oligomers can be mentioned, but the present invention is not limited thereto. It is preferable to use a solvent for the reaction between the starting alcohol and fluorinated olefin.
  • a nonprotonic polar solvent can be used, and specific examples of the solvent include DMF, DMSO, NMP, sulfolane, diglyme, triglyme, ether, THF, chloroform, dichloromethane, and the like. Water may be added to the reaction solution.
  • a basic catalyst may be used as a reaction catalyst or as a scavenger when HF is by-produced. Specific examples of the basic catalyst is KOH, N a OH, K 2 C0 3, N a 2 C 0 3, N a H C0 3 inorganic bases such as, Toryechiruamin, and organic bases such as Toripuchi Ruami down.
  • the reaction temperature is preferably from 10 to 200 ° C, preferably from 0 to 150 ° C, particularly preferably from 10 to 12 CTC, and the reaction pressure is not particularly limited, but is preferably from 0 to 20 kg Zcn 2 G, particularly preferably from 0 to 10 CTC. Performing reactions with kgZcni 2 G it can.
  • the reaction time is 0.5 to 100 hours, preferably 2 to 50 hours.
  • Fluorinated oils (III) can be synthesized in various ways. For example, pentafluoropropionyl fluoride, hexafluoropropylene oxide oligomeric acid fluoride and tetrafluoroxetane are reacted in the presence of a catalyst, and further reacted with an alcohol compound, or reacted or fluorinated. By doing so, a fluorinated oil (III) can be synthesized.
  • the fluorinated oil (III) can be synthesized by reacting, reducing, or fluorinating the obtained compound with an alcohol compound.
  • a non-protonic polar solvent can be used, and specific examples of the solvent include DMF, DMSO, NMF, sulfolane, acetonitrile, diglyme, triglyme, tetraglyme, and crown ether.
  • the reaction catalyst is preferably KF, CsF, KI, KBr or the like.
  • the alcohol compound to be used include lower alcohols such as methyl alcohol and ethyl alcohol, but do not limit the present invention.
  • fluorinated oils may be used not only alone in cosmetics but also in a mixture with two or more kinds or perfluoropolyether.
  • the fluorinated oil of the present invention is used for foundation cosmetics such as foundation, tongue, cheek color and eye color, basic cosmetics such as lotion, emulsion, cream, hair care such as rinse and treatment, lipstick overcoat, UV care It can be used for cosmetics.
  • the fluorine-based oil can be used in an amount of 0.01 to 100% by weight.
  • Cosmetics using fu-hu oil It is manufactured according to the usual method.
  • Fluorinated oil At least one selected from the group consisting of (1), (I I) and (I I I) is 1 to 30% by weight.
  • the balance of the cosmetic is the other ingredients needed to make the cosmetic.
  • the cosmetic contains, as other components, for example, non-fluorinated oils, powders other than powders treated with a fluorine compound, silicone, hydrocarbon-based oils, preservatives, and additives.
  • the content of the fluorinated oil is preferably 2 to 20% by weight, more preferably 5 to 15% by weight.
  • the content of the fluorine compound-treated powder is preferably 5 to 20% by weight, or 70 to 95% by weight.
  • the powder treated with the fluorine compound used in the present invention may be, for example, a polyfluoroalkylphosphoric acid (or a salt thereof), a fluoroalkyldi (oxoxetyl) aminophosphoric acid ester, or a fluoroalkylphosphoric acid ester.
  • a fluorine-containing compound such as a polymer having a barfluoroalkyl group.
  • the polyfluoroalkyl phosphoric acid (or salt thereof) may be as described in US Pat. No. 3,632,744, for example, having the formula:
  • M is a hydrogen atom, an alkali metal, ammonium or substituted ammonium, m and ⁇ are integers of 1 to 20, and the average value of y is 1.0 to 2.5. ] It may be the compound shown by these.
  • Fluoroalkyldi (oxoshethyl) aminophosphates are disclosed in It may be those described in JP-A-2-250074, for example,
  • the fluoroalkyl phosphate may be those described in JP-A-5-124932.
  • n is an integer of 1 to 3
  • ⁇ is an integer of 4 to 20.
  • the polymer having a perfluoroalkyl group may be one described in JP-A-55-167209, and a homopolymer of a (meth) acrylate having a perfluoroalkyl group, or (Meth) acrylate having a perfluoroalkyl group and a monomer having a double bond (eg, acrylate, maleic anhydride, chloroprene, butadiene, methyl vinyl ketone, etc.) It may be united.
  • Examples of the powder to be treated include tanolek, kaolin, mica, titanium mica, titanium oxide, iron oxide, magnesium oxide, zinc monoxide, zinc dioxide, heavy or light calcium carbonate, dibasic calcium phosphate, aluminum hydroxide, Inorganic powders such as barium sulfate, silica, alumina, silica gel, carbon black, antimony oxide, magnesium silicate aluminate, magnesium metasilicate aluminate, and synthetic mica; protein powder, fish foil, metal stone, poly Organic powders such as vinyl chloride, nylon 12, microcrystalline fiber powder, tar dye, lake and the like.
  • the oil may consist only of fluorinated oil, Alternatively, it may be a mixture of a fluorinated oil and a non-fluorinated oil.
  • non-fluorinated oils include solid and semi-solid oils such as cellulose, lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax, tertiary fatty acids, and higher alcohols: squalane, liquid paraffin, ester Fluid oils such as oil, diglyceride, triglyceride, and nilicorn oil.
  • the cosmetic is a powder foundation, mild, cheek color or bright color
  • the powder foundation, bright, cheek color and eye color should be
  • the liquid foundation is
  • the cosmetic is a lotion
  • the lotion is
  • Organic solvent eg, alcohol
  • Alcohol 10% by weight or less
  • Emulsifier 5% by weight or less
  • the alcohol may be a monohydric, dihydric and trihydric alcohol.
  • the emulsion is
  • Emulsifier 5% by weight or less
  • the cosmetic is a cream
  • the cream
  • Emulsifier 10% by weight or less
  • the rinse is:
  • Emulsifier 5% by weight or less
  • the cosmetic is a lipstick overcoat
  • Pentaerythritol (30 g), NaOH (0.9 g) and dimethylsulfoxide (200 mi) were placed in a 500 nil S US autoclave, and the pressure was reduced by purging with methane, and hexafluoropropane (132 g) was added. Was charged. Hexafluoropropane was further introduced each time it was consumed and reacted while the reaction temperature was rising (reaction temperature: 8 CTC). After completion of the reaction (reaction time: 12 hours), the mixture was extracted with HCFC-11b and washed with water, 1N-HC1 aqueous solution, and saturated saline. The organic eyebrow is dried over anhydrous magnesium sulfate, filtered, and the solvent in the cocoa liquid is distilled off under reduced pressure to obtain a colorless oily substance corresponding to 15 Og of the fluorinated oil (I) b:
  • Trimethylolethane (30 g), KOH (49.3 g) and dimethylsulfoxide (150 ml) were placed in a 50 Oml autoclave made of SUS, and the atmosphere was replaced with nitrogen. The pressure was reduced, and tetrafluoroethylene (TFE) (7 5g) was charged. Each time TFE was consumed, it was further introduced and reacted as the reaction temperature rose (reaction temperature: 80 ° C). After the completion of the reaction (reaction time: 8 hours), the mixture was extracted with HCFC-141b and washed with water, a 1N-HC1 aqueous solution, and a saturated saline solution. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent in the filtrate was distilled off under reduced pressure. A colorless oily substance corresponding to 10 Og of the fluorinated oil (I) c:
  • the obtained oil is a compound corresponding to the fluorinated oil (I) d:
  • reaction temperature 20 ° C Gas chromatographic analysis of the reaction mixture revealed that the tetrafluorooxetane beak disappeared.
  • methanol (50 g) was added to the obtained reaction solution, diglyme was removed by distillation under reduced pressure to obtain a colorless oily compound f (15 lg) corresponding to the fluorine-based oil (III).
  • a 300 ml eggplant flask is charged with 67.8 g of polypropylene glycol (molecular weight: 2,000), 4.7 g of pyridine, and 53 g of dichloromethane, and is dropped with a dropping funnel.
  • perfluoroalkyl phosphoric acid ester diethanolamine salt (trade name: Junidyne TG-101 (solid content: 15%), manufactured by Daikin Industries, Ltd.) Dispersion and mixed powder of 133.3 g diluted with 2000 g of water [oxidized A mixture of titanium, yellow iron oxide, red iron oxide, black iron oxide, talc, and sericite in a weight ratio of ls.s / s.szi.ozi-oss.o / i.6] 400 g with a juicer mixer Mix for 3 minutes. After adjusting the pH to 3 or less by adding dilute hydrochloric acid, Suction filtration was performed. The resultant was dried by heating at 60 ° C. for 24 hours and pulverized with a speed cutter for 30 seconds to obtain a fluorine compound-treated powder.
  • the oleophobic properties of the fluorinated oils of Production Examples 1 to 5 (Examples 1 to 5) and Comparative Production Example 1 (Comparative Example 1) were evaluated.
  • the oleophobicity of fluorinated oil was evaluated by adding 5 Omg of fluorinated oil to 5 g of liquid paraffin, shaking and allowing to stand for 10 minutes, and observing the state of the fluorinated oil. .
  • Table 1 shows the evaluation results.
  • Table 3 shows the evaluation results.
  • the fluorine-based oil was applied directly to the skin, and the familiarity with the skin was evaluated according to the following criteria, as compared to the perfluoropolyether of Comparative Example 4.
  • Fluorine-based oil 10 In Table 5, the fluorine compound-treated powder of the components (1) to (6) contains 5% by weight of a perfluoroalkylethyl phosphate ester jetanolamine salt:
  • Components (1) to (7) were mixed and pulverized with an atomizer, transferred to a Henschel mixer, added with component (8), and mixed uniformly. This was placed in a mold and press-molded to form a foundation.
  • Example 16-20 and Comparative Example 7 (Demnum S-20) could be molded by Breath, but Comparative Example 6 [dimethylpolysiloxane (10 Osc)] could not be molded. Further, Example 16-20 is Comparative Example 7 (Demnum S-20) The adhesion of the skin to the skin was better than that of the skin.
  • Perfume 0.1 Component (1) to (4) of the powder treated with a fluorine compound is 5% by weight of perfluoranolecheletchinorellanate estenoresietanolreamine salt:
  • the components (1) to (4) were mixed and pulverized with an atomizer, transferred to a Henschel mixer, and the components (5) to (7) were added and mixed uniformly. This was put into a mold and breath-formed to make a powder foundation.
  • the fluorine compound-treated powder of the components (1) to (4) contains 5% by weight of a perfluoroalkylethyl ester diethanolamine salt:
  • Components (1) to (4) were mixed and pulverized.
  • the resulting mixture of components (5) to (13) was uniformly emulsified to obtain the desired liquid foundation.
  • the components (7) were prepared in Examples 26 to 30 when the fluorine oils of Production Examples 1 to 5 were used, and component (7) was replaced with perfluoroboryl ether (Demnam).
  • Comparative example 9 is the case where S-20) is replaced.
  • Examples 26 to 30 had better adhesion to the skin of Van Daeng Dyeon than Comparative Example 9.
  • the components (1) and (2) were uniformly mixed to obtain a lipstick overcoat.
  • the components (1) were manufactured as in Examples 31 to 35, respectively, with the fluoro oil of Production Example 15 used as the component (1).
  • S-20 manufactured by Daikin Industries, Ltd.
  • Comparative Example 10 Comparative Example 10.
  • the adhesion of the red overcoat to the skin was better than in Comparative Example 10.
  • the components (1) to (9) were dissolved by heating, and the components (10) to (13) dissolved by heating were added, and the mixture was uniformly emulsified and cooled to obtain a desired cream.
  • Example 36 to 40 are based on the case of the fluorine-based oil
  • Comparative Example 11 is a case where the component (6) is replaced with perfluoro-mouth polyether (Demnum S-20 (manufactured by Daikin Industries, Ltd.)).
  • the penetration of the cream into the skin was better than in Comparative Example 11.
  • the components (7) were the fluorine-based oils of Production Examples 1 to 5 as Examples 41 to 45, and the component (7) was used as perfluoropolyether (Demnum S-20 (Daikin Comparative Example 12 is the time when the above was replaced with)).
  • Examples 41-45 had better penetration of skin lotion into the skin than Comparative Example 11.
  • Examples 46 to 50 and Comparative Example 13 (hair rinse)
  • the components (1) to (9) were mixed and dissolved at 80 ° C and allowed to cool to room temperature to obtain a hair rinse.
  • each component (3) was manufactured in the same manner as in Production Example 1.
  • Example 46-50 The case of oil is referred to as Example 46-50, and the case of replacing component (3) with perful ropolier-ter (Demnum S-20) is referred to as Comparative Example 13.
  • Comparative Example 13 the hair penetration of hair was better than that of Comparative Example 13.

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Abstract

Cosmetic preparations which contain fluorinated oils of general formulae (I), (II), (III), do not impair the oil repellency of powdery materials treated with fluorine compounds, and are excellent in compatibility with the skin and inexpensive.

Description

明 細 窖 ッ素系オイルを含有する化粧料  Cosmetics containing fluorinated oils
発明の分野 Field of the invention
本発明は、 フッ素系オイルを含有する化粧料に関する。 本発明は、 炭化 水素系オイルと併用したときに炭化水素系オイルと相溶せず、 また、 フッ 素化合物処理粉体と併用したときに、 フッ素化合物処理粉体の撥油性を阻 害しないフッ素系オイルを含有する化粧料に関する。 このフッ素系オイル は上記の特徴に加えて、 皮 に対する安全性と親和性が高く、 安価である という特徴がある。  The present invention relates to a cosmetic containing a fluorinated oil. The present invention relates to a fluorine-containing compound which is not compatible with a hydrocarbon-based oil when used in combination with a hydrocarbon-based oil, and which does not inhibit the oil repellency of the fluorine-compound-treated powder when used in combination with a fluorine-compound-treated powder. The present invention relates to a cosmetic containing a system oil. This fluorinated oil has the characteristics of high safety and affinity for the skin, and inexpensiveness, in addition to the above characteristics.
関連技術 Related technology
近年、 パーフルォロポリエーテルを配合する化粧料が良く使用されてい る。 パーフルォロボリエーテルは、 炭化水素系オイルと併用したときに炭 化水素系オイルと相溶しない性質 (疎油性)、 および、 フッ素化合物処理粉 体と併用したときに、 フッ素化合物処理粉体の撥油性を阻害しない性質を 有する。 しかし、 パーフルォロポリエーテルは本来、 真空ポンプなどの潤 滑剤として開発された化合物であり、 必ずしも化粧品に配合するのに最適 なものではない。 具体的には、 パーフルォロポリエーテルはボリエーテル の水素が完全にフッ素に置換されているために、 肌への親和性が悪く、 ま た、 非常に高価である。  In recent years, cosmetics containing perfluoropolyether have been widely used. Perfluoropolyether is incompatible with hydrocarbon oils when used in combination with hydrocarbon oils (lipophobic), and when used in combination with fluorine compound treated powders, It does not impair the oil repellency of However, perfluoropolyether is a compound originally developed as a lubricant for vacuum pumps and the like, and is not necessarily optimal for blending into cosmetics. Specifically, perfluoropolyether has a poor affinity for the skin and is very expensive because the hydrogen of the polyether is completely replaced by fluorine.
発明の要旨 Summary of the Invention
本発明の目的は、 フッ素化合物処理粉体と併用したときにフッ素化合物 処理粉体の撥油性を阻害せず、 肌への親和性がよく、 安価であるフッ素系 オイルを提供することにある。 本発明は、 上記の問題を解決するために、 鋭意研究した結果、 特定のフッ 素化オイルが、 パーフルォロボリエ—テルと同等の①疎油性、 ②フッ素化 合物処理粉体の撥油性を阻害しない性質、 ③皮廣に対する安全性を有し、 さらに、 完全にフッ素化していないために、 パーフルォロポリエーテルよ りも④皮廣への親和性が高く、 ⑤安価で製造できることを見い出した。 本発明は、 An object of the present invention is to provide a fluorine-based oil which does not impair the oil repellency of the powder treated with a fluorine compound when used in combination with the powder treated with a fluorine compound, has good affinity for the skin, and is inexpensive. According to the present invention, as a result of intensive research to solve the above-mentioned problems, a specific fluorinated oil has an oil-oleophobicity equivalent to that of perfluoropolyether, and a repellency of fluorinated compound-treated powder. It does not impair oiliness. ③ It is safe against skin, and because it is not completely fluorinated, it has a higher affinity for skin than perfluoropolyether. I found what I could do. The present invention
一般式： ( I )General formula: (I)
Figure imgf000004_0001
Figure imgf000004_0001
[式中、 R1'および R"は、 水素原子、 または部分的にあるいは完全にフッ 素化された ^素数 1〜20の脂肪族基、 Rl bおよび Ι^Ίま、 水素原子、 炭 素数 1~20の脂肪族基、 または部分的にあるいは完全にフッ素化された 炭素数 1〜20の脂肪族基である。 ただし、 R''~Rldの少なくとも 1つ が、 部分的にあるいは完全にフッ素化された炭素数 1〜20の脂肪族基で ある。 nは 1〜20の数である。 ] [Wherein, R 1 'and R "represent a hydrogen atom or a partially or completely fluorinated aliphatic group having a prime number of 1 to 20, R lb and Ι ^ Ί, a hydrogen atom, a carbon number An aliphatic group having 1 to 20 or a partially or completely fluorinated aliphatic group having 1 to 20 carbon atoms, provided that at least one of R '' to R ld is partially or completely Is an aliphatic group having 1 to 20 carbon atoms, and n is a number of 1 to 20.]
で示されるフッ素系オイル （ I ) を 0. 01~100重量％含有すること を特徴とする化粧料を提供する。 A cosmetic comprising 0.01 to 100% by weight of a fluorine-based oil (I) represented by the formula:
加えて、 本発明は、 一般式：
Figure imgf000004_0002
In addition, the present invention provides a compound of the general formula:
Figure imgf000004_0002
[式中、 Rz'は、 水素原子、 部分的にあるいは完全にフッ素化された炭素 数 1〜 20の脂肪族基、 R2b、 尺2'ぉょび1¾"は、 炭衆数 1〜20の脂肪 族基、 部分的にあるいは完全にフッ素化された炭素数 1〜20の脂肪族基 である。 ただし、 R2"〜R2dの少なくとも 1つが部分的にあるいは完全に フッ素化された炭素数 1〜20の脂肪族基である。 mは 1〜20の数であ る。 ] [Wherein, R z ′ is a hydrogen atom, a partially or completely fluorinated aliphatic group having 1 to 20 carbon atoms, R 2b , a shaku 2ぉ 1 ¾ ¾ ”is a coal number 1 to 20 aliphatic groups, partially or fully fluorinated C 1-20 aliphatic groups It is. Provided that at least one of R 2 "to R 2d is a partially or completely fluorinated aliphatic group having a carbon number of 1 to 20. M is Ru number der 1-20.]
で示されるフッ素系オイル （I I) を 0.01〜 100%含有することを 特徴とする化粧料を提供する。 A cosmetic comprising 0.01 to 100% of a fluorine-based oil (II) represented by the formula:
さらに、 本発明は、 一般式：  Further, the present invention provides a compound of the general formula:
CF3 CF 3
XO-(CFCF20)h(CH2CF2CF20)。-Y-COOR3 (川 ) XO- (CFCF 2 0) h ( CH 2 CF 2 CF 2 0). -Y-COOR 3 (river)
[式中、 Xは、 水素原子、 フッ素原子、 塩素原子、 臭素原子または部分的 にあるいは完全にフッ素化された炭素数 1〜30の脂肪族基、 Yは部分的 にあるいは完全にフッ素化された炊素数 1〜30の脂肪族基、 尺3は炭素 数 1〜22の脂肪族基、 h + o=l〜； 100である。] Wherein X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a partially or fully fluorinated aliphatic group having 1 to 30 carbon atoms, and Y is a partially or completely fluorinated group. An aliphatic group having 1 to 30 carbon atoms, a shaku 3 is an aliphatic group having 1 to 22 carbon atoms, h + o = l ~; ]
で示されるフッ素系オイル （I I I) を 0.01〜 100重量％含有する ことを特徴とする化粧料を提供する。 A cosmetic comprising 0.01 to 100% by weight of a fluorinated oil (III) represented by the formula:
さらに加えて、 本発明は、 フッ素系オイル （1)、 (I I) および （I I Γ ) からなる群から選択された少なくとも一種を 1〜30重量％とフッ 素化合物処理粉体を 5~95重量％含有することを特徴とする化粧料を提 供する。  In addition, the present invention provides 1 to 30% by weight of at least one selected from the group consisting of the fluorinated oils (1), (II) and (IIΓ) and 5 to 95% by weight of a fluorine compound-treated powder. % Cosmetics are provided.
発明の詳細な説明 Detailed description of the invention
本発明においては、 フッ素系オイル （1)、 フッ素系オイル （I I) お よび Zまたはフッ素系オイル （I I I) を使用する。  In the present invention, a fluorinated oil (1), a fluorinated oil (II) and Z or a fluorinated oil (III) are used.
一般式 （1)、 （I I) および （I I I) において、 R''、 Rlb、 Rい、 Rld、 R2\ R2\ Rz\ R2d、 X、 Yは、 部分的にあるいは完全にフッ 素化された脂肪族基である場合に、 酸素原子或いは不飽和結合を有してよ い （部分的にフッ素化された脂肪族基は、 例えば、 R】DOCH2基等であつ てよい（R1Dは部分的に或いは完全にフッ素化された脂肪族基 （例えばァ ルキル基） である。）。 部分的にあるいは完全にフッ素化された脂肪族基の 例としては次のものが挙げられる。 In the general formulas (1), (II) and (III), R '', R lb , R, R ld , R 2 \ R 2 \ R z \ R 2d , X and Y are partially or completely When it is a fluorinated aliphatic group, it may have an oxygen atom or an unsaturated bond. (A partially fluorinated aliphatic group is, for example, R] D OCH 2 group, etc. (R 1D is a partially or fully fluorinated aliphatic group (eg, an alkyl group)). Examples of partially or fully fluorinated aliphatic groups include:
-CFH2 -CFH 2
一 C F2H One CF 2 H
-CF3 -CF 3
-CF2C F2H -CF 2 CF 2 H
-CH2C F3 -CH 2 CF 3
一 CF2CFHC F3 One CF 2 CFHC F 3
-CF2CH3 -CF 2 CH 3
一 C F 2C FH2 One CF 2 C FH 2
-C(CF3)2CH3 -C (CF 3 ) 2 CH 3
一 CF2CH(CF3)2 One CF 2 CH (CF 3 ) 2
- C(C F3)2C F2H -C (CF 3 ) 2 CF 2 H
- C(CH3)F C F2C F2C F9 -C (CH 3 ) FCF 2 CF 2 CF 9
-CH2C F2CHzOH -CH 2 CF 2 CH z OH
(C F3)2CF CFHCFC F3 (C F3)2CF C FC FHC Fa (CF 3 ) 2 CF CFHCFC F 3 (CF 3 ) 2 CF C FC FHC Fa
(CF3)ZCCFHC F2CF3 (CF 3 ) Z CCFHC F 2 CF 3
I  I
(CF3)2CHCFC F2CF3 (CF 3 ) 2 CHCFC F 2 CF 3
I  I
(CF3)2CF CFC(C F3)HCF2CFZCF3 (CF3)2CF CFHC(CF3)CF2CF2CF3 ((CF3)2CF)2CCFHCF3 ((C F3)2CF)2CHC FC F3 -CH2CF2COORM (R11は炭素数 1〜： L 0の脂肪族基である。 ）(CF 3 ) 2 CF CFC (CF 3 ) HCF 2 CF Z CF3 (CF 3 ) 2 CF CFHC (CF 3 ) CF 2 CF 2 CF 3 ((CF 3 ) 2 CF) 2 CCFHCF 3 ((CF 3 ) 2 CF) 2 CHC FC F 3 -CH 2 CF 2 COOR M (R 11 is 1 to carbon atoms: an aliphatic group of L 0.)
R'\ Rい、 R2b、 および R2oは、 炭素数 1〜20の脂肪族基であ る場合に、 酸素原子を有してよい。 炭素数 1〜20の脂肪族基の例は、 メ チル、 ェチル、 n—プロピル、 イソプロピル、 n—プチル、 イソブチル、 sec—ブチル、 t一ブチルなどのアルキル基、 ヒ ドロキシメチル、 2—ヒ ドロキシェチル （一 CH2CH2OH) 等のヒ ドロキシアルキル基が挙げら れる。 R 'have \ R, R 2b, and R2o, when Ru der aliphatic group having 1 to 20 carbon atoms and may have an oxygen atom. Examples of the aliphatic group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, hydroxymethyl, and 2-hydroxyxethyl ( And a hydroxyalkyl group such as CH 2 CH 2 OH).
繰り返し単位における Rlb、 Rい、 R2bおよび R2tは各々同一であって も異なっていてもよい。 R lb , R, R 2b and R 2t in the repeating unit may be the same or different.
R1'〜Rld、 R2'〜R2d、 χおよび γにおいて、 好ましい炭素数は、 1In R 1 ′ to R ld , R 2 ′ to R 2 d , χ, and γ, the preferred number of carbon atoms is 1
〜10、 特に 2〜4である。 ~ 10, especially 2 ~ 4.
フッ素系オイル （I) は具体的には次のものが挙げられる。  Specific examples of the fluorinated oil (I) include the following.
RaOCH2CHCH2ORa R a OCH 2 CHCH 2 OR a
OR "as OR "a s
RaO-(CH2CHCH20)2-Ra R a O- (CH 2 CHCH 20 ) 2 -R a
Ra R a
RaO-(CH2CHCH20)3-Ra R a O- (CH 2 CHCH 20 ) 3 -R a
ORB RaO-(CH2CHCH20)4-Ra ORa OR B R a O- (CH 2 CHCH 20 ) 4 -R a OR a
RaO-(CH2CHCH2O)10-Ra R a O- (CH 2 CHCH 2 O) 10 -Ra
ORa OR a
C(CH2ORc)4 C (CH 2 OR c ) 4
CH2ORc CH 2 OR c
Rc-(OCH2C-CH2)2-ORc R c- (OCH 2 C-CH 2 ) 2 -OR c
CH2ORc CH2ORc CH 2 OR c CH 2 OR c
Rc-(OCH2C-CH2)3-ORc R c- (OCH 2 C-CH 2 ) 3 -OR c
CH2ORc CH 2 OR c
CH3C(CH2ORc)3 CH 3 C (CH 2 OR c ) 3
CH3 CH 3
Rc-(OCH2C-CH2)2-ORc R c- (OCH 2 C-CH 2 ) 2 -OR c
CH2ORc CH3 CH 2 OR c CH 3
Rc-(OCH2-C-CH2)3-ORc R c- (OCH 2 -C-CH 2 ) 3 -OR c
CH2ORc (CH3)2C(CH2ORc)2 CH 2 OR c (CH 3 ) 2 C (CH 2 OR c ) 2
CH3CH2C(CH2ORc)3 (CH3CH2)2C(CH2ORc)2
Figure imgf000008_0001
CH 3 CH 2 C (CH 2 OR c ) 3 (CH 3 CH 2 ) 2 C (CH 2 OR c ) 2
Figure imgf000008_0001
C(CH2ORc)2 C (CH 2 OR c ) 2
C2H5 (CH3)2CH C 2 H 5 (CH 3 ) 2 CH
C(CH2ORc)2 C (CH 2 OR c ) 2
CH3 CH 3
〔式中、 それぞれの R aおよび R cは、 同一または異なって、 一 CF2CF2H、 [In the formula, each of R a and R c is the same or different, and one CF 2 CF 2 H,
- C F2CFHCF3、 -CF 2 CFHCF 3 ,
一 C F2CH3、 One CF 2 CH 3 ,
一 CF2CFH2、 One CF 2 CFH 2 ,
一 C(CF3)2CH3、 One C (CF 3 ) 2 CH 3 ,
一 CF2CH(CF3)2、 One CF 2 CH (CF 3 ) 2 ,
一 C(CF3)2C F2H、 One C (CF 3 ) 2 CF 2 H,
一 C(CH3)FCF2CF2CF3である。 ] One is C (CH 3 ) FCF 2 CF 2 CF 3 . ]
フッ素系オイル （ I I) は具体的には次のものが举げられる,  Fluorinated oils (II) include the following,
Figure imgf000009_0001
Figure imgf000009_0001
Figure imgf000009_0002
Figure imgf000010_0001
Figure imgf000009_0002
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000010_0002
Figure imgf000010_0003
Figure imgf000010_0003
[式中、 それぞれの Rbは  Where each Rb is
一 C F2C F2H、 One CF 2 CF 2 H,
-CF2CFHCF3、 -CF 2 CFHCF 3 ,
一 C F2CH3 One CF 2 CH 3
— C FaCFH2、 — CF a CFH 2 ,
一 C(CF3)2CH3、 One C (CF 3 ) 2 CH 3 ,
— CF2CH(CF3)2、 — CF 2 CH (CF 3 ) 2 ,
一 C(C F3)2CF2H、 One C (CF 3 ) 2 CF 2 H,
一 C(CH3)FC F2CF2CF3である。 ] One C (CH 3) a FC F 2 CF 2 CF 3. ]
フッ素系オイル （ I I I ) は具体的には次のものが挙げられる, C3F7OC(CF3)FCF20(CH2CF2CF20)nCH2CF2C02CH3 Specific examples of the fluorinated oil (III) include the following, C 3 F 7 OC (CF 3 ) FCF 20 (CH 2 CF 2 CF 20 ) n CH 2 CF 2 C0 2 CH 3
[nの平均値 = 10]  [Average value of n = 10]
C3F70C(CF3)FCF2O(CIl2CF2CjF20)nCH2CF2C02CH3 C 3 F 7 0C (CF 3 ) FCF 2 O (CIl 2 CF 2 CjF 20 ) n CH 2 CF 2 C0 2 CH 3
[nの平均値 =20]  [Average value of n = 20]
C3F70C(CF3)FCF20(CH2CFZCF20)„CH2CFZC02CH3 C 3 F70C (CF 3) FCF 2 0 (CH 2 CF Z CF 2 0) "CH 2 CF Z C0 2 CH3
[ηの平均値 =30] C3F70C(CF3)FCF20(CH2CF2CF20)nCH2CF2C02CH3 [Average value of η = 30] C 3 F 7 0 C (CF 3 ) FCF 2 0 (CH 2 CF 2 CF 2 0) n CH 2 CF 2 C0 2 CH 3
[nの平均値 =50]  [Average value of n = 50]
C3F70C(CF3)FCF20(CH2CF2CF2O)nCH2CF2CO2CH2CH3 C 3 F 7 0 C (CF 3 ) FCF 20 (CH 2 CF 2 CF 2 O) n CH 2 CF 2 CO 2 CH 2 CH 3
[nの平均値 = 10]  [Average value of n = 10]
C3F70C(CF3)FCF20(CH2CF2CF20)„CH2CF2C02C3HT C 3 F 7 0C (CF 3 ) FCF 2 0 (CH 2 CF 2 CF 2 0) „CH 2 CF 2 C0 2 C 3 H T
[nの平均値 =10]  [Average value of n = 10]
C3F7OC(CF3)FCF20(CH2CF2CF20)„CH2CF2C02CH(CH3)2 C 3 F 7 OC (CF 3 ) FCF 20 (CH 2 CF 2 CF 20 ) „CH 2 CF 2 C0 2 CH (CH 3 ) 2
[nの平均値 = 10]  [Average value of n = 10]
C3F70(C(CF3)FCF20)m(CH2CF2CF20)„CH2CF2C02CH3 C 3 F 7 0 (C (CF 3 ) FCF 20 ) m (CH 2 CF 2 CF 20 ) 0CH 2 CF 2 C0 2 CH 3
[nの平均値 =10、 mの平均値 =2]  [Average value of n = 10, Average value of m = 2]
C3F70(C(CF3)FCF20)ra(CH2CF2CF20)nCH2CF2C02CH3 C 3 F 7 0 (C (CF 3 ) FCF 20 ) ra (CH 2 CF 2 CF 20 ) n CH 2 CF 2 C0 2 CH 3
[nの平均値 =10、 mの平均値 =3]  [Average value of n = 10, Average value of m = 3]
フッ素系オイル （I) は様々な方法で合成することができる。 例えば原 料となるアルコール化合物とフルォロォレフィ ンを反応させることによつ て、 フッ素系オイル （I) を合成することができる。 原料となるアルコー ル化合物としては、 種々挙げられる力く、 グリセリン、 ジグリセリン、 ポリ グリセリン、 一般的にヒンダードアルコール、 ヒンダードアルコールオリ ゴマーと呼ばれている化合物が挙げられるが本発明を限定するものではな い。 原料アルコールとフルォロォレフィンとの反応には溶媒を用いるのが よい。 溶媒については、 非プロ トン性極性溶媒を用いることができ、 溶媒 の具体例としては DMF (ジメチルホルムアミ ド） 、 DMSO (ジメチル スルホキンド）、 NMP (N—メチルピロリ ドン）、 スルホラン、 ジグライ ム、 トリグライム、 エーテル、 THF、 クロ口ホルム、 ジクロロメタン、 メチルェチルケトン、 アセトンなどがある。 また反応溶液には水を加えて もよい。 反応触媒、 あるいは HFが副生する場合その捕捉剤として、 塩基 性触媒を用いてもよい。 塩基性触媒の具体例としては、 KOH、 N aOH. K2C03、 Na2C03、 N aHC03などの無機塩基、 トリヱチルァミン、 トリプチルァミンなどの有機塩基などがある。 Fluorinated oil (I) can be synthesized by various methods. For example, a fluorine-based oil (I) can be synthesized by reacting a raw material alcohol compound with fluorofluorin. Examples of the alcohol compound as a raw material include various compounds such as glycerin, diglycerin, polyglycerin, and compounds generally called hindered alcohols and hindered alcohol oligomers, which limit the present invention. Not a thing. It is preferable to use a solvent for the reaction between the starting alcohol and fluorofluorin. As the solvent, a non-protonic polar solvent can be used. Specific examples of the solvent include DMF (dimethylformamide), DMSO (dimethyl sulfokind), NMP (N-methylpyrrolidone), sulfolane, diglyme, and triglyme. , Ether, THF, chloroform, dichloromethane, methyl ethyl ketone, acetone, etc. Water may be added to the reaction solution. When a reaction catalyst or HF is produced as a byproduct, a base is used as a scavenger. A neutral catalyst may be used. Specific examples of the basic catalyst is KOH, N aOH. K 2 C0 3, Na 2 C0 3, N aHC0 such third inorganic bases, Toriwechiruamin, and organic bases such as Toripuchiruamin.
反応温度は一 10〜200°C、 好ましくは 0〜150°C,特に好ましく は 10〜120°Cがよく、 反応圧力は特に限定されないが好ましくは 0~ 20kgZcm2G (ゲージ圧）、 特に好ましくは 0〜； I 0 kgZcm2Gで反応を 行うことができる。 反応時間は 0.5〜100時間、 好ましくは 2〜50 時間とするのがよい。 The reaction temperature is preferably from 10 to 200 ° C, preferably from 0 to 150 ° C, particularly preferably from 10 to 120 ° C. The reaction pressure is not particularly limited, but is preferably from 0 to 20 kgZcm 2 G (gauge pressure), particularly preferably. Is 0 to; I 0 kgZcm 2 G. The reaction time is 0.5 to 100 hours, preferably 2 to 50 hours.
フッ素系オイル （ I I) は様々な方法で合成することができる。 例えば 原料となるアルコール化合物とフルォロォレフィ ンを反応させることによ. てフッ素系オイル （I I) を合成することができる。 原料となるアルコ一 ル化合物としては、 種々挙げられるが、 一般的にヒンダードアルコール、 ヒンダ一ドアルコールオリゴマーと呼ばれている化合物が挙げられるが、 本発明を限定するものではない。 原料アルコールとフルォロォレフインと の反応には溶媒を用いるのがよい。 溶媒については、 非プロ トン性極性溶 媒を用いることができ、 溶媒の具体例としては DMF、 DMSO、 NMP, スルホラン、 ジグライム、 トリグライム、 エーテル、 THF、 クロ口ホル ム、 ジクロロメタンなどがある。 また反応溶液には水を加えてもよい。 反 応触媒、 あるいは HFが副生する場合その捕捉剤として、 塩基性触媒を用 いてもよい。 塩基性触媒の具体例としては、 KOH、 N a OH, K2C03, N a 2C 03、 N a H C03などの無機塩基、 トリェチルァミン、 トリプチ ルァミ ンなどの有機塩基などがある。 Fluorinated oil (II) can be synthesized by various methods. For example, a fluorine-based oil (II) can be synthesized by reacting an alcohol compound as a raw material with a fluororefin. There are various examples of the alcohol compound as a raw material, and compounds generally referred to as hindered alcohols and hindered alcohol oligomers can be mentioned, but the present invention is not limited thereto. It is preferable to use a solvent for the reaction between the starting alcohol and fluorinated olefin. As the solvent, a nonprotonic polar solvent can be used, and specific examples of the solvent include DMF, DMSO, NMP, sulfolane, diglyme, triglyme, ether, THF, chloroform, dichloromethane, and the like. Water may be added to the reaction solution. A basic catalyst may be used as a reaction catalyst or as a scavenger when HF is by-produced. Specific examples of the basic catalyst is KOH, N a OH, K 2 C0 3, N a 2 C 0 3, N a H C0 3 inorganic bases such as, Toryechiruamin, and organic bases such as Toripuchi Ruami down.
反応温度は一 10〜200°C、 好ましくは 0〜150°C、 特に好ましく は 10〜12 CTCがよく、 反応圧力は特に限定されないが、 好ましくは 0 〜20kgZcn2G、 特に好ましくは 0〜10 kgZcni2Gで反応を行うことが できる。 反応時間は 0.5〜100時間、 好ましくは 2〜50時間とする のがよい。 The reaction temperature is preferably from 10 to 200 ° C, preferably from 0 to 150 ° C, particularly preferably from 10 to 12 CTC, and the reaction pressure is not particularly limited, but is preferably from 0 to 20 kg Zcn 2 G, particularly preferably from 0 to 10 CTC. Performing reactions with kgZcni 2 G it can. The reaction time is 0.5 to 100 hours, preferably 2 to 50 hours.
フッ素系オイル （I I I ) は様々な方法で合成することができる。 例え ば触媒存在下、 ペンタフルォロプロピオニルフルオリ ド、 へキサフルォロ プロピレンォキサイ ドオリゴマー酸フロリ ドとテトラフルォロォキセタン を反応させ、 さらにアルコール化合物と反応、 あるいは通元、 あるいはフッ 素化を行うことによって、 フッ素系オイル （I I I ) を合成することがで きる。 また、 反応に予めハロゲン化アルカリ金属開始剤もしくは、 アル力 リ金属フッ化物とァシルフルオリ ドの共存開始剤を用いてテトラフルォロ ォキセタンを開環重合せしめた系にへキサフルォロプロピレンォキシドを 仕込み、 得られた化合物をアルコール化合物と反応、 あるいは還元、 ある いはフッ素化を行うことによって、 フッ素系オイル （ I I I ) を合成する ことができる。 溶媒については、 非プロ トン性極性溶媒を用いることがで き、 溶媒の具体例としては DMF、 DMSO、 NMF、 スルホラン、 ァセ トニ卜リル、 ジグライム、 トリグライム、 テトラグライム、 クラウンエー テルなどがある。 反応触媒は KF、 C s F、 K I、 KB r等が好ましい。 使用するアルコール化合物としては、 メチルアルコール、 ェチルアルコ一 ル等の低級アルコールが挙げられるが本発明を限定するものではない。  Fluorinated oils (III) can be synthesized in various ways. For example, pentafluoropropionyl fluoride, hexafluoropropylene oxide oligomeric acid fluoride and tetrafluoroxetane are reacted in the presence of a catalyst, and further reacted with an alcohol compound, or reacted or fluorinated. By doing so, a fluorinated oil (III) can be synthesized. Hexafluoropropylene oxide was previously charged to a system in which tetrafluoroxetane was subjected to ring-opening polymerization using an alkali metal halide initiator or an initiator coexisting with alkali metal fluoride and acyl fluoride in the reaction, The fluorinated oil (III) can be synthesized by reacting, reducing, or fluorinating the obtained compound with an alcohol compound. As the solvent, a non-protonic polar solvent can be used, and specific examples of the solvent include DMF, DMSO, NMF, sulfolane, acetonitrile, diglyme, triglyme, tetraglyme, and crown ether. . The reaction catalyst is preferably KF, CsF, KI, KBr or the like. Examples of the alcohol compound to be used include lower alcohols such as methyl alcohol and ethyl alcohol, but do not limit the present invention.
これらのフッ素系オイルは単独で化粧品に配合するだけでなく、 2種類 以上のものやパーフルォロポリエ一テルと混合して用いてもよい。 本発明 のフッ素系オイルは、 ファンデーション、 おしろい、 チークカラー、 アイ カラーなどの仕上化粧品、 化粧水、 乳液、 クリームなどの基礎化粧品、 リ ンス、 トリー トメ ン トなどのヘアケア、 口紅オーバーコート、 UVケア化 粧品などに、 使用できる。 化粧料において、 フッ素系オイルは 0.01 ~ 100重量％の配合量で使用できる。 フッ衆系オイルを使用した化粧品は 通常の方法に従って製造される。 These fluorinated oils may be used not only alone in cosmetics but also in a mixture with two or more kinds or perfluoropolyether. The fluorinated oil of the present invention is used for foundation cosmetics such as foundation, tongue, cheek color and eye color, basic cosmetics such as lotion, emulsion, cream, hair care such as rinse and treatment, lipstick overcoat, UV care It can be used for cosmetics. In cosmetics, the fluorine-based oil can be used in an amount of 0.01 to 100% by weight. Cosmetics using fu-hu oil It is manufactured according to the usual method.
本発明の化粧料は、  The cosmetic of the present invention,
(a) フッ素系オイル （1)、 （I I) および （I I I) からなる群から 選択された少なくとも一種を 1〜30重釐％と  (a) Fluorinated oil At least one selected from the group consisting of (1), (I I) and (I I I) is 1 to 30% by weight.
( b ) フッ素化合物処理粉体を 5 ~ 95重量％  (b) 5 to 95% by weight of fluorine compound treated powder
含有する場合に待に有効である。 It is effective for waiting when it contains.
化粧料の残部は、 化粧料とするのに必要な他の成分である。 化粧料は、 他の成分として、 例えば、 非フッ素系オイル、 フッ素化合物処理粉体以外 の粉体、 ンリコーン、 炭化水素系オイル、 防腐剤または番料などを含有す る。  The balance of the cosmetic is the other ingredients needed to make the cosmetic. The cosmetic contains, as other components, for example, non-fluorinated oils, powders other than powders treated with a fluorine compound, silicone, hydrocarbon-based oils, preservatives, and additives.
フッ素系オイルの含有量は、 2~20重量％、 より好ましくは 5〜15 重量％であることが好ましい。  The content of the fluorinated oil is preferably 2 to 20% by weight, more preferably 5 to 15% by weight.
フッ素化合物処理粉体の含有量は、 5〜20重量％、 または 70〜95 重量％であることが好ましい。  The content of the fluorine compound-treated powder is preferably 5 to 20% by weight, or 70 to 95% by weight.
本発明において使用するフッ素化合物処理粉体は、 粉体を例えばポリフ ルォロアルキルリ ン酸 （またはその塩）、 フルォロアルキルジ（ォキシェチ ル）ァミ ンリ ン酸エステル、 フルォロアルキルリ ン酸エステル、 バーフル ォロアルキル基を有する重合体などのフッ素化合物で処理して得られる。 ポリフルォロアルキルリン酸 （またはその塩） は、 米国特許第 3632 744号に記載されているものであってよく、 例えば、 式：  The powder treated with the fluorine compound used in the present invention may be, for example, a polyfluoroalkylphosphoric acid (or a salt thereof), a fluoroalkyldi (oxoxetyl) aminophosphoric acid ester, or a fluoroalkylphosphoric acid ester. And a fluorine-containing compound such as a polymer having a barfluoroalkyl group. The polyfluoroalkyl phosphoric acid (or salt thereof) may be as described in US Pat. No. 3,632,744, for example, having the formula:
[CroF2„,+1CnH2„0],PO(OM)3-y [C ro F 2 „, +1 C n H 2 „ 0], PO (OM) 3 - y
[式中、 Mは水素原子、 アルカリ金属、 アンモニゥムまたは置換アンモニ ゥム、 mおよび πは 1〜20の整数、 yの平均値は 1.0~2.5である。] で示される化合物であつてよい。  [In the formula, M is a hydrogen atom, an alkali metal, ammonium or substituted ammonium, m and π are integers of 1 to 20, and the average value of y is 1.0 to 2.5. ] It may be the compound shown by these.
フルォロアルキルジ（ォキシェチル）ァミ ンリ ン酸エステルは、 特開昭 6 2- 250074号公報に記載されているものであってよく、 例えば、 式 Fluoroalkyldi (oxoshethyl) aminophosphates are disclosed in It may be those described in JP-A-2-250074, for example,
[CnF2n + i CH2CHzO]qPO[O CH2)(CH2CH2OH) 2] 3-, [式中、 nは 1〜20の整数、 qは 1または 2である。 ] [C n F 2 n + i CH2CH z O] q PO [O CH 2 ) (CH 2 CH 2 OH) 2 ] 3-, [where n is an integer from 1 to 20, and q is 1 or 2 . ]
で示される化合物であつてよい。 And the compound represented by
フルォロアルキルリン酸エステルは、 特開平 5— 124932号公報に 記載されているものであってよく、 例えば、 式：  The fluoroalkyl phosphate may be those described in JP-A-5-124932.
(CF 2„ +1 C H2CH20)mPO(OH)3-m (CF 2 „ + 1 CH 2 CH 20 ) m PO (OH) 3 - m
[式中、 mは 1〜3の整数、 πは 4〜20整数である。 ]  [In the formula, m is an integer of 1 to 3, and π is an integer of 4 to 20. ]
で示される化合物であってよい。 May be a compound represented by
パーフルォロアルキル基を有する重合体は、 特開昭 55— 167209 号公報に記載されているものであってよく、 パーフルォロアルキル基を有 する （メタ）ァクリレートの単独重合体、 またはパーフルォロアルキル基 を有する （メタ）ァクリレー卜と二重結合を有する単量体 （例えば、 ァク リル酸エステル、 無水マレイン酸、 クロ口プレン、 ブタジエン、 メチルビ 二ルケトンなど） との共重合体であってよい。  The polymer having a perfluoroalkyl group may be one described in JP-A-55-167209, and a homopolymer of a (meth) acrylate having a perfluoroalkyl group, or (Meth) acrylate having a perfluoroalkyl group and a monomer having a double bond (eg, acrylate, maleic anhydride, chloroprene, butadiene, methyl vinyl ketone, etc.) It may be united.
被処理粉体としては、 例えば、 タノレク、 カオリン、 雲母、 雲母チタン、 酸化チタン、 酸化鉄、 酸化マグネシウム、 一酸化亜鉛、 二酸化亜鉛、 重質 もしくは軽質炭酸カルシウム、 第 2燐酸カルシウム、 水酸化アルミニウム、 硫酸バリウム、 シリカ、 アルミナ、 シリカゲル、 カーボンブラック、 酸化 アンチモン、 ケィ酸アルミ ン酸マグネシウム、 メタケイ酸アルミ ン酸マグ ネンゥム、 合成雲母などの無機粉末；蛋白質粉末、 魚鳞箔、 金属石钹、 ポ リ塩化ビニル、 ナイロン 12、 微結晶繊維粉末、 タール色素、 レーキなど の有機粉末等などが挙げられる。  Examples of the powder to be treated include tanolek, kaolin, mica, titanium mica, titanium oxide, iron oxide, magnesium oxide, zinc monoxide, zinc dioxide, heavy or light calcium carbonate, dibasic calcium phosphate, aluminum hydroxide, Inorganic powders such as barium sulfate, silica, alumina, silica gel, carbon black, antimony oxide, magnesium silicate aluminate, magnesium metasilicate aluminate, and synthetic mica; protein powder, fish foil, metal stone, poly Organic powders such as vinyl chloride, nylon 12, microcrystalline fiber powder, tar dye, lake and the like.
下記の化粧料において、 オイルは、 フッ素系オイルのみからなってよく、 あるいはフッ紫系オイルと非フッ素系オイルとの混合物であってよい。 非フッ素系オイルの例は、 ヮセリ ン、 ラノ リ ン、 セレシン、 マイクロク リスタリ ンワックス、 カルナゥバロウ、 キャンデリラロウ、 髙級脂肪酸、 高級アルコール等の固形 ·半固形油： スクヮラン、 流動パラフィ ン、 エス テル油、 ジグリセライ ド、 トリグリセライ ド、 ンリコーン油等の流動油で あ O。 In the following cosmetics, the oil may consist only of fluorinated oil, Alternatively, it may be a mixture of a fluorinated oil and a non-fluorinated oil. Examples of non-fluorinated oils include solid and semi-solid oils such as cellulose, lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax, tertiary fatty acids, and higher alcohols: squalane, liquid paraffin, ester Fluid oils such as oil, diglyceride, triglyceride, and nilicorn oil.
化粧料がパウダーファンデーション、 おしろい、 チークカラーまたはァ イカラーである場合に、 パウダーファンデーショ ン、 おしろい、 チーク力 ラーおよびアイカラーは、  If the cosmetic is a powder foundation, mild, cheek color or bright color, the powder foundation, bright, cheek color and eye color should be
オイル 1 ~ 3 0重量％、 Oil 1 to 30% by weight,
フッ素化合物処理粉体 5〜 9 5重 S%、 Fluorine compound treated powder 5 ~ 5 5% S%,
シリコーン処理粉体および/または未処理粉体 5〜 9 5重量％、 防腐剤 1重量％以下、 5% to 95% by weight of siliconized powder and / or untreated powder, less than 1% by weight of preservative,
香料 1重童％以下 Fragrance 1% child or less
からなつてよい。 You can be
化粧料がリキッ ドファンデーションである場合に、 リキッ ドファ ンデー ショ ンは、  If the cosmetic is a liquid foundation, the liquid foundation is
オイル 1 ~ 1 0重量％、 Oil 1-10% by weight,
フッ素化合物処理粉体 5〜3 0重量％、 Fluorine compound treated powder 5-30% by weight,
シリコーン処理粉体および または未処理粉体 5 ~ 3 0重量％、 水溶性高分子 1重量％以下、 5 to 30% by weight of siliconized powder and / or untreated powder, 1% by weight or less of water-soluble polymer,
水 8 0重量％以下、 80% by weight or less of water,
防腐剤 1重量％以下、 Preservatives 1% by weight or less,
香料 1重量％以下 Perfume 1% by weight or less
からなつてよい。 化粧料が、 化粧水である場合に、 化粧水は、 You can be When the cosmetic is a lotion, the lotion is
オイル 0. 0 1〜 1 0重量％、 Oil 0.01 to 10% by weight,
有機溶媒 （例えば、 アルコール） 1 0重量％以下、 Organic solvent (eg, alcohol) 10% by weight or less,
乳化剤 5重量％以下、 Emulsifier 5% by weight or less,
防腐剤 1重量％以下、 Preservatives 1% by weight or less,
香料 1重量％以下、 Perfume 1% by weight or less,
水 9 9重量％以下 Water 9 9% by weight or less
からなつてよい。 アルコールは、 一価アルコール、 2価アルコールおよび 3価アルコールであってよい。 You can be The alcohol may be a monohydric, dihydric and trihydric alcohol.
化粧料が乳液である場台に、 乳液は、  On the platform where the cosmetic is emulsion, the emulsion is
オイル 0. 0 1〜2 0重量％、 Oil 0.0 1-2% by weight,
乳化剤 5重量％以下、 Emulsifier 5% by weight or less,
防腐剤 1重量％以下、 Preservatives 1% by weight or less,
香料 1重量％以下 Perfume 1% by weight or less
水 9 5重量％以下 Water 95% by weight or less
からなつてよい。 You can be
化粧料がクリームである場合に、 クリームは、  When the cosmetic is a cream, the cream
オイル 0. 0 1〜9 5重量％、 Oil 0.0 1 ~ 95 5% by weight,
乳化剤 1 0重量％以下、 Emulsifier 10% by weight or less,
防腐剤 1重量％以下、 Preservatives 1% by weight or less,
香料 1重量％以下、 Perfume 1% by weight or less,
水 8 0重量％以下 Water 80% by weight or less
からなつてよい。 You can be
化粧料がリ ンスである場合に、 リ ンスは、  If the cosmetic is a rinse, the rinse is:
オイル 0 . 0 1〜 1 0重量％、 カチォン性界面活性剤 10重量％以下、 Oil 0.1 to 10% by weight, Cationic surfactant 10% by weight or less,
乳化剤 5重量％以下、 Emulsifier 5% by weight or less,
防腐剤 1重量％以下、 Preservatives 1% by weight or less,
香料 1重量％以下、 Perfume 1% by weight or less,
水 95重量％以下 Water 95% by weight or less
からなつてよい。 You can be
化粧料が口紅オーバーコートである場合に、  If the cosmetic is a lipstick overcoat,
オイル 80〜： I 00重量％、 Oil 80 ~: I 00% by weight,
シリ力粉末および/またはアルミナ粉末 20重量％以下 Sili powder and / or alumina powder 20% by weight or less
からなつてよい。 You can be
発明の好ましい態様 Preferred embodiments of the invention
本発明の実施例について具体的に説明するが、 この説明が本発明を限定 するものではない。  Examples of the present invention will be specifically described, but this description does not limit the present invention.
製造例 1 [オイル a (フッ素系オイル （1) に相当）の製造] Production example 1 [Production of oil a (corresponding to fluorinated oil (1))]
50 Omlの S US製ォ一卜クレーブにジグリセリ ン （55.4g)、 ジメ チルスルホキンド（30 Oml)および KOH(l Og)を仕込み、 室温で撹拌 しながら液相部にテトラフルォロエチレン（TFE) を圧力 4kgZcn2 · G となるように仕込んだ。 10時間撹拌 （反応温度 80 °C) の後、 未反応の TF Eをパージしクロ口ホルムを 10 Onl加えた後、 5 %H C1水溶液お よび 10%NaHCO3水溶液で洗浄し、 無水硫酸マグネシウムで乾燥して 濾過し濾液中の溶媒を减圧下に留去して 138. Ogのフッ素系オイル （ I ) に相当する無色油状物 a ： Diglycerin (55.4 g), dimethyl sulfokind (30 Oml) and KOH (lOg) were charged into a 50 Oml SUS autoclave, and tetrafluoroethylene (TFE) was added to the liquid phase while stirring at room temperature. Was charged to a pressure of 4 kgZcn 2 · G. After stirring for 10 hours (reaction temperature 80 ° C), unreacted TFE was purged, 10 mL of chloroform was added, and the mixture was washed with 5% aqueous HCl and 10% aqueous NaHCO 3 and dried over anhydrous magnesium sulfate. And the solvent in the filtrate is distilled off under reduced pressure to give a colorless oil corresponding to 138. Og of the fluorinated oil (I) a:
HCF2CF20-(CH2CHCH2-0)2CF2CF2H HCF 2 CF 2 0- (CH 2 CHCH2-0) 2 CF 2 CF 2 H
OCF2CF2H OCF 2 CF 2 H
か得られた。 CT Or obtained. CT
製造例 2 [オイル b (フッ素系オイル （ I ) に相当）の製造] Production Example 2 [Production of oil b (corresponding to fluorine-based oil (I))]
500 nilの S US製ォートクレーブにペンタエリスリ トール （30g)、 N a OH ( 0.9 g) およびジメチルスルホキシド （200mi) を入れ室素 置換を行い减圧にしたところへ、 へキサフルォロプロパン （132g) を 仕込んだ。 へキサフルォロプロパンが消費される毎にさらに導入し反応温 度が上昇するままに反応した （反応温度： 8 CTC)。 反応終了 （反応時間 ： 12時間） 後、 HCFC— 1 1 bにて抽出し、 水、 1 N— HC1水溶 液、 および飽和食塩水にて洗净した。 有機眉を無水硫酸マグネシウムにて 乾燥、 濾過し、 澳液中の溶媒を減圧下に留去して 15 Ogのフッ素系オイ ル （ I ) に相当する無色油状物 b ：  Pentaerythritol (30 g), NaOH (0.9 g) and dimethylsulfoxide (200 mi) were placed in a 500 nil S US autoclave, and the pressure was reduced by purging with methane, and hexafluoropropane (132 g) was added. Was charged. Hexafluoropropane was further introduced each time it was consumed and reacted while the reaction temperature was rising (reaction temperature: 8 CTC). After completion of the reaction (reaction time: 12 hours), the mixture was extracted with HCFC-11b and washed with water, 1N-HC1 aqueous solution, and saturated saline. The organic eyebrow is dried over anhydrous magnesium sulfate, filtered, and the solvent in the cocoa liquid is distilled off under reduced pressure to obtain a colorless oily substance corresponding to 15 Og of the fluorinated oil (I) b:
C(CH2〇 C F2C FH C F3)4 C (CH 2 〇 CF 2 C FH CF 3 ) 4
が得られた。 was gotten.
製造例 3 [オイル c (フッ素系オイル （I ) に相当）の製造] Production example 3 [Production of oil c (corresponding to fluorinated oil (I))]
50 Omlの SU S製オー トクレーブにトリメチロールェタン （30g)、 KOH (49.3g)およびジメチルスルホキシド （ 150ml) を入れ窒素 置換を行い減圧にしたところへ、 テトラフルォロエチレン （TFE) (7 5g) を仕込んだ。 TFEが消費される毎にさらに導入し反応温度が上昇 するままに反応した （反応温度： 80°C)。 反応終了 （反応時間： 8時間） 後、 HCFC— 141 bにて抽出し、 水、 1N— HC1水溶液、 および飽 和食塩水にて洗浄した。 有機層を無水硫酸マグネシウムにて乾燥、 '慮過し、 濾液中の溶媒を減圧下に留去して 10 Ogのフッ素系オイル （ I ) に相当 する無色油状物 c ：  Trimethylolethane (30 g), KOH (49.3 g) and dimethylsulfoxide (150 ml) were placed in a 50 Oml autoclave made of SUS, and the atmosphere was replaced with nitrogen. The pressure was reduced, and tetrafluoroethylene (TFE) (7 5g) was charged. Each time TFE was consumed, it was further introduced and reacted as the reaction temperature rose (reaction temperature: 80 ° C). After the completion of the reaction (reaction time: 8 hours), the mixture was extracted with HCFC-141b and washed with water, a 1N-HC1 aqueous solution, and a saturated saline solution. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent in the filtrate was distilled off under reduced pressure. A colorless oily substance corresponding to 10 Og of the fluorinated oil (I) c:
CH3C(CH2OCF2CF2H)3 CH 3 C (CH 2 OCF 2 CF 2 H) 3
が得られた。 was gotten.
製造例 4 [オイル d (フッ素系オイル 〔1 ) に相当）とオイル e (フッ索系ォ ィル （I I) に相当）の混合物の製造] Production example 4 [Oil d (corresponding to fluorine-based oil [1]) and oil e (cordless) Production of a mixture of (II))
1 Lオー トクレープにジペンタエリスリ トール （150g)、 KOH (3 9g)、 ジメチルスルホキシド （45 Oral) を入れ窒素置換を行い減圧にし たところへ、 テトラフルォロエチレン （TFE) (437g) を仕込んだ。 TF Eが消費される毎にさらに導入し 80°Cにて 12時間反応した。 反応 終了後、 HCFC— 14 lbにて抽出し、 水、 1NHC1水溶液、 飽和食塩 水にて洗浄した。 有機層を無水硫酸ナトリウムにて乾燥、 濾過した後 50 °Cにて減圧濃縮し無色オイル状化合物 （435 g) を得た。  Dipentaerythritol (150 g), KOH (39 g), and dimethyl sulfoxide (45 Oral) were placed in a 1 L autoclave, and the atmosphere was replaced with nitrogen. The pressure was reduced, and tetrafluoroethylene (TFE) (437 g) was charged. Each time TFE was consumed, it was further introduced and reacted at 80 ° C for 12 hours. After completion of the reaction, the mixture was extracted with HCFC—14 lb, and washed with water, 1N HCl aqueous solution, and saturated saline. The organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure at 50 ° C to obtain a colorless oily compound (435 g).
得られたオイルは、 フッ素系オイル （I) に該当する化合物 d ：  The obtained oil is a compound corresponding to the fluorinated oil (I) d:
Figure imgf000020_0001
とフッ素系オイル （ I I ) に該当する化合物 e ：
Figure imgf000020_0001
And compounds corresponding to fluorinated oils (II) e:
Figure imgf000020_0002
Figure imgf000020_0002
を含有し化合物 dZeの重量比は 67/33であった。 And the weight ratio of compound dZe was 67/33.
製造例 5 [オイル f (フッ素系オイル （I I I) に相当）の製造] Production Example 5 [Production of oil f (corresponding to fluorinated oil (I I I))]
1 Lのフラスコ中に、 事前に脱水したジグライム （50 Oml) と、 乾燥 した CsF(15.2g) を入れて撹拌しておく。 そこへ、 C3F7OC(CF3)In a 1 L flask, put diglyme (50 Oml), which has been previously dehydrated, and dried CsF (15.2 g), and stir. There, C 3 F 7 OC (CF 3 )
FCOF(6FOダイマー）（33.2g) を加えて均一になるまで撹拌し、 テトラフル才ロォキセタン （ 130 g) を少量ずつ滴下して反応させた。FCOF (6FO dimer) (33.2 g) was added and the mixture was stirred until uniform, and tetrafluroxetane (130 g) was added dropwise little by little to react.
20時間にわたる滴下の終了後、 2時間撹拌した （反応温度 20°C) 後、 反応液をガスクロ分析したところ、 テトラフルォロォキセタンのビークが 消失した。 得られた反応液にメタノール （50g)を加えたのち、 減圧蒸 留にてジグライムを除いたところ、 フッ素系オイル （ I I I ) に該当する 無色オイル状化合物 f (15 lg)が得られた。 After dropping over 20 hours, the mixture was stirred for 2 hours (reaction temperature 20 ° C), Gas chromatographic analysis of the reaction mixture revealed that the tetrafluorooxetane beak disappeared. After methanol (50 g) was added to the obtained reaction solution, diglyme was removed by distillation under reduced pressure to obtain a colorless oily compound f (15 lg) corresponding to the fluorine-based oil (III).
化合物 f ： C3F70C(CF3)FCF20(CIIzCF2CF20)nCH2CF2C02CH3 Compound f: C 3 F 7 0 C (CF 3 ) FCF 20 (CII z CF 2 CF 20 ) n CH 2 CF 2 C0 2 CH 3
[nの平均値 = 103  [Average of n = 103
比較製造例 1 [疎油性のないフッ素系オイル（6 FO)3 P PG] Comparative production example 1 [Fluoro oil (6 FO) 3 P PG without oleophobicity]
300mlナスフラスコにポリプロピレングリコール（分子量 2, 000) 67.8g ピリジン 4. 7 g、 ジクロロメタン 53 gを仕込み、 滴下ロート で  A 300 ml eggplant flask is charged with 67.8 g of polypropylene glycol (molecular weight: 2,000), 4.7 g of pyridine, and 53 g of dichloromethane, and is dropped with a dropping funnel.
CF3CF2CF2O-(CFCF20)3-CF-C ,Ρ CF 3 CF 2 CF 2 O- (CFCF 2 0) 3-CF-C, Ρ
CF3 CF3 CF 3 CF 3
[以下、 （6FO)3という] [Hereafter referred to as (6FO) 3]
を滴下した。 室温で 2時間撹拌後、 0.1N塩酸水溶液と精製水で洗净し、 硫酸マグネシウムで乾燥して下記の構造式を有する（6 F 0)3 PPGを得 た。 Was added dropwise. After stirring at room temperature for 2 hours, the mixture was washed with a 0.1N aqueous hydrochloric acid solution and purified water, and dried over magnesium sulfate to obtain (6F0) 3 PPG having the following structural formula.
CF3CF2CF20-(CFCF20)3-CFCOO-(CHCH20)35-CH3 CF 3 CF 2 CF 2 0- ( CFCF 2 0) 3 -CFCOO- (CHCH 2 0) 35 -CH 3
CF3 CF3 CH3 製造例 6 (フッ素化合物処理粉体の製造） CF 3 CF 3 CH 3 Production Example 6 (Production of fluorinated powder)
市販のパーフルォロアルキルリ ン酸エステルジエタノールァミン塩 [商 品名ュニダイン TG— 101(固形分 15%)、 ダイキン工業製] 133.3 gを水 2000 gで希釈した分散液と混合粉体 [酸化チタン、 黄酸化鉄、 ベンガラ、 黒酸化鉄、 タルク、 セリサイ トを ls.s/s.szi.ozi- o ss.o/ i.6の重量比で混合したもの] 400gをジューサーミ キサ一で 3分間混合した。 希塩酸を添加して、 pHを 3以下に調製した後、 吸引濾過した。 6 0 °Cで 2 4時間加熱乾燥し、 スピー ドカッターで 3 0秒 間粉砕して、 フッ素化合物処理粉体とした。 Commercially available perfluoroalkyl phosphoric acid ester diethanolamine salt (trade name: Junidyne TG-101 (solid content: 15%), manufactured by Daikin Industries, Ltd.) Dispersion and mixed powder of 133.3 g diluted with 2000 g of water [oxidized A mixture of titanium, yellow iron oxide, red iron oxide, black iron oxide, talc, and sericite in a weight ratio of ls.s / s.szi.ozi-oss.o / i.6] 400 g with a juicer mixer Mix for 3 minutes. After adjusting the pH to 3 or less by adding dilute hydrochloric acid, Suction filtration was performed. The resultant was dried by heating at 60 ° C. for 24 hours and pulverized with a speed cutter for 30 seconds to obtain a fluorine compound-treated powder.
実施例 1〜 5および比絞例 1 (疎油性の評価） Examples 1 to 5 and Comparative Example 1 (Evaluation of oleophobicity)
製造例 1〜5 (実施例 1〜5 ) と比較製造例 1 (比較例 1 ) のフッ素系 オイルの疎油性を評価した。 疎油性はフッ素系オイル 5 O mgを流動パラフィ ン 5 g中に添加して振り混ぜて 1 0分間放置し、 フッ素系オイルの状態を 観察することにより、 フッ¾系オイルの疎油性を評価した。  The oleophobic properties of the fluorinated oils of Production Examples 1 to 5 (Examples 1 to 5) and Comparative Production Example 1 (Comparative Example 1) were evaluated. The oleophobicity of fluorinated oil was evaluated by adding 5 Omg of fluorinated oil to 5 g of liquid paraffin, shaking and allowing to stand for 10 minutes, and observing the state of the fluorinated oil. .
〇： 疎油性あり （フッ素系オイルが完全に沈降する）  〇: oleophobic (fluorine oil completely settles out)
Δ ： 疎油性少しあり （フッ素系オイルが分散する）  Δ: slightly oleophobic (fluorine-based oil is dispersed)
X ： 疎油性なし （フッ素系オイルが溶解する）  X: No oleophobicity (fluorine oil dissolves)
評価結果を表丄に示す。  Table 1 shows the evaluation results.
表 1 . 疎油性  Table 1. Oleophobicity
実施例 製造例 m 疎油性 実施例 1 製造例 1 オイル a 〇 実施例 2 製造例 2 オイル b 〇 実施例 3 製造例 3 オイルに 〇 実施例 4 製造例 4 オイル d +オイル e 〇 実施例 5 製造例 5 オイル f 〇 比較例 1 比較製造例 1 疎油性のないフッ素系オイル X Example Production Example m Oil lipophobic Example 1 Production Example 1 Oil a 〇 Example 2 Production Example 2 Oil b 〇 Example 3 Production Example 3 Oil 〇 Example 4 Production Example 4 Oil d + Oil e 〇 Example 5 Production Example 5 Oil f 比較 Comparative Example 1 Comparative Production Example 1 Non-oleophobic fluorinated oil X
(C6F0)3PPG) 一  (C6F0) 3PPG) I
実施例 6〜 1 0および比較例 2 (フッ素化合物処理粉体の撥油性を阻害し ない性質の評価） Examples 6 to 10 and Comparative Example 2 (Evaluation of properties that do not inhibit oil repellency of powder treated with a fluorine compound)
製造例 1—5 (実施例 6— 1 0 ) と比較製造例 1 (比較例 2 ) のフッ素 系オイル 1 0 0 gと製造例 6のフッ素化合物処理粉体 9 0 0 gをヘンシェル ミキサ一で混合したものについて撥油性試験を行った。  100 g of the fluorinated oil of Production Example 1-5 (Example 6-10) and Comparative Production Example 1 (Comparative Example 2) and 900 g of the fluorine compound-treated powder of Production Example 6 were mixed with a Henschel mixer. The mixture was subjected to an oil repellency test.
撩油性試験：據羝の上に粉体を均一に塗布し、 表 2に示す表面張力の異な る 8種類の油を滴下する。 Xにならない点数 （滴下後 1分後に、 完全にし みこまない油の点数） を撥油性とする。 Sharpness test: Apply powder uniformly on the base and drop 8 types of oils with different surface tensions as shown in Table 2. Points that do not become X (one minute after dropping, completely Oil repellent).
判疋基準 Standard
〇：完全にはじく。  〇: Completely repels.
X ：滴下後、 1分後に ：兀全 V しみ >_ ¾_1  X: 1 minute after dripping: all V-stains> _ ¾_1
表
Figure imgf000023_0001
い ffl table
Figure imgf000023_0001
Do ffl
f 点数 種類 (25て）  f Points type (25)
1 流動 くラフィン 31.2  1 Fluid Kurafin 31.2
2 HDZ流動パラフィ ン 29.6  2 HDZ liquid paraffin 29.6
3 へキサデ力ン（HD) 27.3  3 Hexadene force (HD) 27.3
4 テトラテカン 26.7  4 Tetratecan 26.7
5 ドデカン 25.0  5 Dodecane 25.0
6 デカン 23.5  6 Decane 23.5
7 オクタン 21.8  7 Octane 21.8
8 ヘプタン 20.0  8 Heptane 20.0
評価結果を表 3に示す。  Table 3 shows the evaluation results.
表 3. フッ素化合物処理粉体の撥油性を阻害しない性質 実施例 製造例 名称 撥油性 実施例 6 製造例 1 才ィノレ a 5 実施例 7 製造例 2 オイル b 5 実施例 8 製造例 3 オイル c 5 実施例 9 製造例 4 オイル d+オイル e 5 実施例 10 製造例 5 オイル 5 比較例 2 比較製造例 1 碟油性のないフッ素系オイル  Table 3. Properties that do not hinder the oil repellency of the fluorine compound-treated powder Example Production example Name Oil repellency Example 6 Production example 1 year old a5 Example 7 Production example 2 Oil b5 Example 8 Production example 3 Oil c5 Example 9 Production Example 4 Oil d + Oil e 5 Example 10 Production Example 5 Oil 5 Comparative Example 2 Comparative Production Example 1
((6FO)3PPG)  ((6FO) 3PPG)
フッ素化合物処理粉体のみ 5 実施例 11~15および比較例 3 5(皮 Itへの親和性の評価）  Fluorine compound-treated powder only 5 Examples 11 to 15 and Comparative Example 3 5 (Evaluation of affinity to leather It)
製造例 1 5(実施例 11 15)と比較製造例 1 (比較例 3) のフッ素 系オイル、 および、 市販のパーフルォロポリエーテルである Fomblin HC-0 4 (モンテフルォス社製） （比較例 4)、 デムナム S— 20 (ダイキン工業 株式会社製） （比較例 5 ) の皮 Itへの親和性を評価した。 フッ素系オイル を直接肌に塗布し、 比较例 4のパーフル才ロポリエーテルと比較して、 皮 ¾へのなじみを以下の基準で評価した。 Fluorinated oils of Production Example 15 (Example 11 15) and Comparative Production Example 1 (Comparative Example 3), and a commercially available perfluoropolyether, Fomblin HC-04 (manufactured by Montefluos) (Comparative Example 4), Demnum S-20 (Daikin Industries) (Comparative Example 5) was evaluated for its affinity for leather It. The fluorine-based oil was applied directly to the skin, and the familiarity with the skin was evaluated according to the following criteria, as compared to the perfluoropolyether of Comparative Example 4.
皮膚が非常に良い場合： 〇〇  If the skin is very good: 〇〇
良い場合： 〇  If good: 〇
同等： △  Equivalent: △
やや劣る場合： X  If inferior: X
非常に劣る場合： X X  Very poor: X X
評価は官能評価の専門パネラー 5名が行い、 その平均を結果とした。 評 価結果を表 4に示す。  The evaluation was performed by five panelists specialized in sensory evaluation, and the average was used as the result. Table 4 shows the evaluation results.
表 4 . 皮 ISとの親和性  Table 4. Affinity with leather IS
実施例 製造例 名称 親和性 実施例 1 1 製造例 1 オイル a 〇〇 実施例 1 2 製造例 2 オイル b 〇〇 実施例 1 3 製造例 3 オイル c 〇〇 実施例 1 4 製造例 4 オイル d +オイル e 0〇 実施例 1 5 製造例 5 オイル 〇〇 比較例 3 比較製造例 1 疎油性のないフッ素系オイル 〇〇 Example Production example Name Affinity Example 1 1 Production example 1 Oil a 〇〇 Example 1 2 Production example 2 Oil b 実 施 Example 1 3 Production example 3 Oil c 〇〇 Example 1 4 Production example 4 Oil d + Oil e 0 〇 Example 1 5 Production Example 5 Oil 〇〇 Comparative Example 3 Comparative Production Example 1 Fluorophilic oil without oleophobic property 〇〇
((6FO)3PPG)  ((6FO) 3PPG)
比較例 4 Forablin HC-04 厶 比絞例 5 デムナム S— 2 0 厶 Comparative Example 4 Forablin HC-04 mm Specific Example 5 Demnum S—20 mm
実施例 16~20ならびに比較例 6および 7 (パウダーファンデ一ショ ン） 表 5. パウダーファンデーショ ン Examples 16 to 20 and Comparative Examples 6 and 7 (Powder Foundation) Table 5. Powder Foundation
原料名 重量％ Raw material name wt%
( 1 ) フッ素化合物処理酸化チタン 10(1) Fluorine compound-treated titanium oxide 10
(2) フッ素化合物処理黄酸化鉄 2.3 (2) Fluorine compound-treated yellow iron oxide 2.3
(3) フッ素化合物処理ベンガラ 0.65 (3) Bengala treated with fluorine compound 0.65
(4) フッ素化合物処理黒酸化鉄 0.35(4) Black iron oxide treated with fluorine compound 0.35
(5) フッ素化合物処理セリサイ ト 20(5) Fluoro compound treated sericite 20
(6) フッ素化合物処理タルク 56.6 (6) Fluorine compound treated talc 56.6
( 7 ) 防腐剤 0.1  (7) Preservative 0.1
(8) フッ素系オイル 10 表 5において、 成分 （1)〜（6) のフッ素化合物処理粉体は、 5重量％ のパーフルォロアルキルェチルリン酸エステルジェタノ一ルァミン塩：  (8) Fluorine-based oil 10 In Table 5, the fluorine compound-treated powder of the components (1) to (6) contains 5% by weight of a perfluoroalkylethyl phosphate ester jetanolamine salt:
O II  O II
(CmF2m+1CH2CH20)nP【ONH2《CH2CH2OH)2】3-n (C m F 2m + 1 CH 2 CH 2 0) n P [ONH 2 << CH 2 CH 2 OH) 2 ] 3-n
(mの平均値 =3.5、 πの平均値 =1.7) (Average value of m = 3.5, Average value of π = 1.7)
で処理されたものである。 It has been processed in.
成分 （1)〜（7) をアトマイザ一で混合粉砕し、 これをヘンシェルミキ サ一に移して、 成分 （8) を加え、 均一に混合した。 これを金型に入れ、 プレス成型して、 ノくウダ一ファンデーションとした。  Components (1) to (7) were mixed and pulverized with an atomizer, transferred to a Henschel mixer, added with component (8), and mixed uniformly. This was placed in a mold and press-molded to form a foundation.
表 5に示す組成のパウダーファンデーンョンにて、 成分（8)がそれぞれ 製造例 1一 5のフッ素系オイルのときを実施例 16— 20とし、 成分（8) をジメチルポリシロキサン （l OOsc) に置き換えたときを比較例 6、 パ 一フルォロポリエーテル （デムナム S— 20) に置き換えたときを比較例 7とする。 実施例 16— 20、 比較例 7 (デムナム S— 20) はブレス成 型可能であつたが、 比較例 6 [ジメチルポリシロキサン（10 Osc)] は成 型できなかった。 また、 実施例 16— 20は比較例 7 (デムナム S— 20) よりもファンデーンョンの皮膚への密着性が良好であつた。 In the powder foundation having the composition shown in Table 5, the components (8) were the fluorinated oils of Production Example 1-15 as Examples 16-20, and the component (8) was dimethylpolysiloxane (100 sc). )), And Comparative Example 7 when replaced with perfluoropolyether (Demnum S-20). Example 16-20 and Comparative Example 7 (Demnum S-20) could be molded by Breath, but Comparative Example 6 [dimethylpolysiloxane (10 Osc)] could not be molded. Further, Example 16-20 is Comparative Example 7 (Demnum S-20) The adhesion of the skin to the skin was better than that of the skin.
実施例 21~25および比較例 8 (アイカラー） Examples 21 to 25 and Comparative Example 8 (eye color)
表 6. アイカラー  Table 6. Eye color
原料名 重量％ Raw material name wt%
(1) フッ素化合物処理雲母チタン 5(1) Fluorine compound treated mica titanium 5
(2) フッ素化合物処理セリサイ ト 29.8 (2) Fluorine compound treated sericite 29.8
(3) フッ素化合物処理マイ力 25 (3) Fluorine compound treatment
(4) フッ素化合物処理着色顔料 25(4) Fluorine compound treated color pigment 25
(5) フッ素系オイル 15(5) Fluorine oil 15
( 6 ) 防腐剤 0. 1 (6) Preservatives 0.1
(7) 香料 0. 1 成分 （1)〜（4) のフッ素化合物処理粉体は、 5重量％のパーフルォロ ァノレキルェチノレリ ン酸エステノレジエタノーノレア ミ ン塩 ：  (7) Perfume 0.1 Component (1) to (4) of the powder treated with a fluorine compound is 5% by weight of perfluoranolecheletchinorellanate estenoresietanolreamine salt:
o  o
II  II
(CmF2m+1CH2CH20)nP[ONH2(CH2CH2OH)2)3.n (C m F 2m + 1 CH 2 CH 2 0) n P [ONH 2 (CH 2 CH 2 OH) 2) 3. N
(mの平均値 =3.5、 nの平均値 = 1.7) (Average value of m = 3.5, Average value of n = 1.7)
で処理されたものである。 It has been processed in.
成分 （1)〜（4) をアトマイザ一で混合粉砕し、 これをヘンシェルミキ サ一に移して、 成分 （5)〜（7) を加え、 均一に混合した。 これを金型に 入れ、 ブレス成型して、 パウダーファンデーションとした。  The components (1) to (4) were mixed and pulverized with an atomizer, transferred to a Henschel mixer, and the components (5) to (7) were added and mixed uniformly. This was put into a mold and breath-formed to make a powder foundation.
表 6に示す組成のアイカラーにて、 成分 （5) がそれぞれ製造例 1一 5 のフッ素系オイルのときを実施例 21— 25とし、 成分 （5) をバーフル ォロポリエーテル （デムナム S— 20) に置き換えたときを比較例 8とす る。 実施例 21 -25は比較例 8よりもアイカラーの皮膚への密着性が良 好であった。  In the eye color of the composition shown in Table 6, when the component (5) was the fluorine-based oil of Production Example 15 as Example 21-25, the component (5) was added to the verfluoropolyether (Demnum S-20). The replacement is referred to as Comparative Example 8. Examples 21 to 25 exhibited better eye color adhesion to skin than Comparative Example 8.
実施例 26〜30および比較例 9 (リキッ ドフ ァ ンデーンョ ン）— 表 7. リキッ ドファンデーンョ ン Examples 26 to 30 and Comparative Example 9 (Liquid Foundation) Table 7. Liquid Foundation
原料名 重量％ Raw material name wt%
(1) フッ素化合物処理酸化チタン 2.2(1) Fluorine compound treated titanium oxide 2.2
(2) フッ素化合物処理酸化鉄 （赤、 黒、 黄） 0.7(2) Fluorine compound treated iron oxide (red, black, yellow) 0.7
(3) フッ素化合物処理セリサイ 卜 5 (3) Fluorite treated sericite 5
(4) フッ素化合物処理タルク 12.1 (4) Fluorine-treated talc 12.1
( 5 ) 防腐剤 0.1(5) Preservative 0.1
(6) スクヮラン 2 (6) Squalane 2
(7) フッ素系オイル 10  (7) Fluorine-based oil 10
(8) ソルビタンモノォレー ト 1  (8) Sorbitan monolate 1
(9) 蔗糖脂肪酸エステル （HLB 16) 2  (9) Sucrose fatty acid ester (HLB 16) 2
(10) カルボキシビ二ルポリマー （1%水溶液） 40  (10) Carboxyvinyl polymer (1% aqueous solution) 40
( 11 ) グリセリ ン 7  (11) Glycerin 7
(12) 香料 0.1 (12) Fragrance 0.1
(13) 精製水 17.8 成分 （1)〜（4) のフッ素化合物処理粉体は、 5重量％のパーフルォロ アルキルェチルリ ン酸エステルジエタノールァミ ン塩 ： (13) Purified water 17.8 The fluorine compound-treated powder of the components (1) to (4) contains 5% by weight of a perfluoroalkylethyl ester diethanolamine salt:
O II  O II
(CmF2m+1CH2CH20)nP[ONH2(CH2CH2OH)2]3-n (C m F 2m + 1 CH 2 CH 2 0) n P [ONH 2 (CH 2 CH 2 OH) 2 ] 3-n
(mの平均値 =3.5、 nの平均値 =1.7) (Average value of m = 3.5, Average value of n = 1.7)
で処理されたものである。 It has been processed in.
成分（1)〜（4)を混合粉砕した。 これに、 成分（5)〜（13)を均一混合 したものを均一に乳化して、 目的のリキッ ドファンデーションを得た。 表 7に示す組成のリキッ ドファンデーションにて、 成分（7)がそれぞれ 製造例 1一 5のフッ素系オイルのときを実施例 26— 30とし、 成分（7) をパーフルォロボリエーテル （デムナム S— 20) に置き換えたときを比 較例 9とする。 実施例 26— 30は比較例 9よりもファンデーンョンの皮 廣への密着性が良好であつた。  Components (1) to (4) were mixed and pulverized. The resulting mixture of components (5) to (13) was uniformly emulsified to obtain the desired liquid foundation. In the liquid foundation having the composition shown in Table 7, the components (7) were prepared in Examples 26 to 30 when the fluorine oils of Production Examples 1 to 5 were used, and component (7) was replaced with perfluoroboryl ether (Demnam). Comparative example 9 is the case where S-20) is replaced. Examples 26 to 30 had better adhesion to the skin of Van Daeng Dyeon than Comparative Example 9.
実施例 31-35および比較例 10 (口紅オーバーコート） 表 8. 口紅ォ一バーコ一ト Examples 31-35 and Comparative Example 10 (lipstick overcoat) Table 8. Lipstick Bar Coat
原料名 重量％  Raw material name wt%
(1) フッ素系オイル 98  (1) Fluorine-based oil 98
(2) シリカ _2_  (2) Silica _2_
成分 （1)および （2) を均一に混合し、 口紅オーバーコートを得た。 表 8に示す組成の口紅オーバーコートにて、 成分 （1) がそれぞれ製造 例 1一 5のフッ素系オイルのときを実施例 31— 35とし、 成分 （1) を パーフルォロポリエーテル （デムナム S— 20 (ダイキン工業株式会社製）） に置き換えたときを比較例 10とする。 実施例 31— 35は比較例 10よ りも Π紅オーバーコートの皮 への密着性が良好であった。  The components (1) and (2) were uniformly mixed to obtain a lipstick overcoat. In the lipstick overcoat having the composition shown in Table 8, the components (1) were manufactured as in Examples 31 to 35, respectively, with the fluoro oil of Production Example 15 used as the component (1). S-20 (manufactured by Daikin Industries, Ltd.)) is referred to as Comparative Example 10. In Examples 31 to 35, the adhesion of the red overcoat to the skin was better than in Comparative Example 10.
実施例 36〜40および比較例 11 (クリーム） Examples 36 to 40 and Comparative Example 11 (cream)
表 9. クリーム  Table 9. Cream
原料名 重量％ Raw material name wt%
( 1 ) N—ス ί了 0ィルー L—グルタミン酸ナトリウム 0.4  (1) N-Success Done 0 E L-Sodium glutamate 0.4
(2) セチルアルコール 3  (2) Cetyl alcohol 3
(3) ワセリン 3  (3) Vaseline 3
(4) ステアリン酸モノグリセライ ド 3  (4) Stearic acid monoglyceride 3
( 5 ) ラノリン 3  (5) Lanolin 3
(6) フッ素系オイル 10  (6) Fluorine-based oil 10
(7) ソルビタンセスキォレー ト 0.5  (7) Sorbitan sesquiate 0.5
(8) ポリオキンエチレンポ オキシプ 0ピレンブ 0フク:！ポリマ- (ブル π二-ノク F-68) 3  (8) Polyoxyethylene ethylene oxide 0 pyrenbu 0 fuku :! Polymer (Bull π2-Noku F-68) 3
(9) 香料 0. 1  (9) Fragrance 0.1
(10) 1, 3—ブチレングリコール 8  (10) 1,3-butylene glycol 8
(11) 防腐剤 0. 1  (11) Preservatives 0.1
( 12 ) グリセリン 10  (12) Glycerin 10
(13) 精製水 残部  (13) Remaining purified water
成分 （1)~(9) を加熱溶解したものに、 加熱溶解した成分 （1 0)〜（1 3) を加え、 均一に乳化し、 冷却して目的のクリームを得た。  The components (1) to (9) were dissolved by heating, and the components (10) to (13) dissolved by heating were added, and the mixture was uniformly emulsified and cooled to obtain a desired cream.
表 9に示す組成のクリームにて、 成分 （6) がそれぞれ製造例 1—5の フッ素系オイルのときを実施例 36— 40とし、 成分 （6) をパーフルォ 口ポリエーテル （デムナム S— 20(ダイキン工業株式会社製）） に置き換 えたときを比較例 11とする。 実施例 36-40は比較例 11よりもクリ —ムの皮廇への浸透性が良好であった。 In the cream having the composition shown in Table 9, component (6) was used in Production Examples 1-5 Examples 36 to 40 are based on the case of the fluorine-based oil, and Comparative Example 11 is a case where the component (6) is replaced with perfluoro-mouth polyether (Demnum S-20 (manufactured by Daikin Industries, Ltd.)). In Example 36-40, the penetration of the cream into the skin was better than in Comparative Example 11.
実施例 41〜 45および比較例 12 (化粧水） Examples 41 to 45 and Comparative Example 12 (Lotion)
表 10. 化粧水  Table 10. Lotion
原料名 重量％ Raw material name wt%
(1) ポリオキシュチレン（20)ゾルビタンモノラウレ-ト 0.4  (1) Polyoxythylene (20) sorbitan monolaurate 0.4
(2) 香料 3  (2) Fragrance 3
(3) エタノール 3  (3) Ethanol 3
(4) 1, 3—ブチレングリコール 3  (4) 1,3-butylene glycol 3
(5) グリセリン 3  (5) Glycerin 3
(6) 防腐剤 10  (6) Preservative 10
(7) フッ素系オイル 0.5  (7) Fluorine oil 0.5
( 8 ) 精製水 残部  (8) Remaining purified water
成分 （1)~(3)、 (7) を混合溶解した。 これを成分 （4)、 （5) 、 (6) および（8) を混合溶解したものに加え、 均一に混合して目的の化 ffi水を得た。  Components (1) to (3) and (7) were mixed and dissolved. This was added to the mixed and dissolved components (4), (5), (6) and (8) and mixed uniformly to obtain the desired chemical water.
表 10の組成の化粧水にて、 成分 （7) がそれぞれ製造例 1—5のフッ 素系オイルのときを実施例 41一 45とし、 成分 （7) をパーフルォロボ リエーテル （デムナム S— 20 (ダイキン工業株式会社製）） に置き換えた ときを比較例 12とする。 実施例 41—45は比較例 11よりも化粧水の 皮癍への浸透性が良好であった。 実施例 46〜50および比較例 13 (ヘアリ ンス） In the lotion having the composition shown in Table 10, the components (7) were the fluorine-based oils of Production Examples 1 to 5 as Examples 41 to 45, and the component (7) was used as perfluoropolyether (Demnum S-20 (Daikin Comparative Example 12 is the time when the above was replaced with)). Examples 41-45 had better penetration of skin lotion into the skin than Comparative Example 11. Examples 46 to 50 and Comparative Example 13 (hair rinse)
ヘアリ ンス  Hair rinse
原料名 重 Raw material name
( 1 ) 塩化ステアリルトリメチルァンモニゥム  (1) Stearyl trimethylammonium chloride
(2) セチルアルコール  (2) Cetyl alcohol
(3) フッ素系オイル  (3) Fluorine-based oil
(4) 防腐剤  (4) Preservative
(5) グリセリン  (5) Glycerin
(6) 香料  (6) Fragrance
(7) 色素  (7) Dye
(8) ポリオキシエチレン（10)'ノルビタンモノォレエ-ト  (8) Polyoxyethylene (10) 'norbitan monooleate
( 9 ) 精製水  (9) Purified water
成分 （1)〜（9) を 80°Cにて混合溶解し、 室温まで放冷してヘアリン スを得た。  The components (1) to (9) were mixed and dissolved at 80 ° C and allowed to cool to room temperature to obtain a hair rinse.
ヒ記のヘアリンスにて、 成分 （3) がそれぞれ製造例 1残微適適残— 35のフッ素系 量量部量部 2325 5552205 32.  In the hair rinse described above, each component (3) was manufactured in the same manner as in Production Example 1.
オイルのときを実施例 46— 50とし、 成分 （3) をパーフル才ロポリエ —テル （デムナム S— 20) に置き換えたときを比較例 13とする。 実施 例 46— 50は比铰例 13よりもへァリンスの髮への浸透性が良好であつ た。 The case of oil is referred to as Example 46-50, and the case of replacing component (3) with perful ropolier-ter (Demnum S-20) is referred to as Comparative Example 13. In Examples 46 to 50, the hair penetration of hair was better than that of Comparative Example 13.
実施例 51〜55および比較例 14 (サンスクリーン乳液） Examples 51 to 55 and Comparative Example 14 (Sunscreen emulsion)
表 12. サンスク リーン乳液  Table 12. Sanskleen emulsion
原料名 重量％ Raw material name wt%
( 1 ) ォクタメチルシクロテ トラシロキサン  (1) Octamethylcyclotetrasiloxane
(2) フッ素系オイル  (2) Fluorine-based oil
(3) ジ チルポリシ Dキサン-ポリオキ'ン了ルキレン共重合体  (3) Ditylpoly-D-xane-polyoxylene-terminated alkylene copolymer
(4) グリセリ ン  (4) Glycerin
(5) ェタノール  (5) Ethanol
(6) フッ素化合物処理酸化亜鉛  (6) Fluorine compound treated zinc oxide
(7) メ トキシ桂皮酸ォクチル  (7) octyl methoxycinnamate
(8) 香料  (8) Fragrance
(9) 水 成分 （6) のフッ素化合物処理粉体は、 7%のパーフルォロアルキルェ チルリ ン酸エステルジエタノールァミ ン塩 ： (9) Water The fluorine compound-treated powder of component (6) contains 7% of perfluoroalkylethyl phosphate diethanolamine salt:
o  o
II  II
(CmF2rn+1CH2CH20)nP[ONH2(CH2CH2OH)2]3.n (C m F 2rn + 1 CH 2 CH 2 0) n P [ONH 2 (CH 2 CH 2 OH) 2] 3. N
(mの平均値 =3.5、 nの平均値 = 1.7) (Average value of m = 3.5, Average value of n = 1.7)
で処理されたものである。 It has been processed in.
成分 （1)〜（3) を室温にて混合溶解し、 成分 （6) を添加しディスパ 一で分散させる。 水相を撹拌しながら添加して乳化し、 目的のサンスクリ ーン乳液を得た。  Mix and dissolve components (1) to (3) at room temperature, add component (6), and disperse with a disperser. The aqueous phase was added with stirring and emulsified to obtain the desired sunscreen emulsion.
上記のサンスクリーン乳液にて、 成分 （2) がそれぞれ製造例 1—5の フッ素系オイルのときを実施例 51— 55とし、 成分 （2) をパ一フルォ 口ポリエーテル （デムナム S— 20(ダイキン工業株式会社製）） に置き換 えたときを比較例 14とする。 実施例 51—55は比較例 14よりも、 皮 廣への密着性、 耐水性が良好であった。  In the above sunscreen emulsion, when the component (2) was the fluorinated oil of Production Example 1-5, each of Examples 51-55 was used. Comparative Example 14 is the time when it was replaced with). Examples 51-55 had better adhesion to skin and better water resistance than Comparative Example 14.

Claims

請 求 の 範 囲 The scope of the claims
1. —般式： ( I )1. —General formula: (I)
Figure imgf000032_0001
Figure imgf000032_0001
[式中、 R1'および R "は、 水素原子、 または部分的にあるいは完全にフッ 素化された炭素数 1~20の脂肪族基、 Rl bおよび R1'は、 水素原子、 炭 素数 1〜20の脂肪族基、 または部分的にあるいは完全にフッ素化された 炭素数 1~20の脂肪族基である。 ただし、 Rle〜R "の少なくとも 1つ カ^ 部分的にあるいは完全にフッ素化された炭素数 1〜20の脂肪族基で ある。 nは 1〜20の数である。 ] [Wherein, R 1 ′ and R ”represent a hydrogen atom or a partially or completely fluorinated aliphatic group having 1 to 20 carbon atoms, and R lb and R 1 ′ represent a hydrogen atom or a carbon number. An aliphatic group having 1 to 20 or a partially or completely fluorinated aliphatic group having 1 to 20 carbon atoms, provided that at least one of R le to R "is partially or completely It is a fluorinated aliphatic group having 1 to 20 carbon atoms. n is a number from 1 to 20. ]
で示されるフッ素系オイル （ I ) を 0.01〜100重量％含有すること を特徴とする化粧料。 A cosmetic comprising 0.01 to 100% by weight of the fluorinated oil (I) represented by the formula (1).
2. —股式： ( II ) 2. —Crotch type: (II)
Figure imgf000032_0002
Figure imgf000032_0002
[式中、 R2'は、 水素原子、 部分的にあるいは完全にフッ素化された炭素 数 1〜20の脂肪族基、 R2b、 R2 'および R2dは、 炭素数 1~20の脂肪 族基、 部分的にあるいは完全にフッ素化された炭素数 1〜20の脂肪族基 である。 ただし、 R24〜R2eの少なくとも 1つが部分的にあるいは完全に フッ素化された炭素数 1〜 20の脂肪族基である。 mは 1〜 20の数であ る。 ] [Wherein, R 2 ′ is a hydrogen atom, a partially or fully fluorinated aliphatic group having 1 to 20 carbon atoms, and R 2b , R 2 ′ and R 2d are a C 1 to C 20 fat. An aliphatic group is a partially or completely fluorinated aliphatic group having 1 to 20 carbon atoms. However, at least one of partially or completely fluorinated aliphatic group having a carbon number 1 to 20 of R 24 to R 2e. m is a number from 1 to 20. ]
で示されるフッ素系オイル （ I I ) を 0.01〜 100%含有することを 特徴とする化粧料。 Containing 0.01 to 100% of the fluorinated oil (II) Characterized cosmetics.
3. 一般式：  3. General formula:
CF3 CF 3
I I
XO-(CFCFzO)h(CH2CF2CF20)0-Y-COOR3 ( III ) XO- (CFCF z O) h (CH 2 CF 2 CF 20 ) 0 -Y-COOR 3 (III)
[式中、 Xは、 水素原子、 フッ素原子、 塩素原子、 臭素原子または部分的 にあるいは完全にフッ素化された炭素数 1~30の脂肪族基 Yは、 は 炭素数 1〜 22の脂肪族基、 h+o=l〜l 00である。] [Wherein, X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a partially or completely fluorinated aliphatic group having 1 to 30 carbon atoms, Y is an aliphatic group having 1 to 22 carbon atoms Group, h + o = l-l00. ]
で示されるフッ素系オイル （I I I) を 0.01〜 100重量％含有する ことを特徴とする化粧料。 A cosmetic comprising 0.01 to 100% by weight of a fluorine-based oil (III) represented by the formula:
4. フッ素系オイル （ I )、 （I I) および （I I I) からなる群から 選択された少なくとも一種を 1〜30重量％とフッ索化合物処理粉体を 5 〜 95重量％含有することを特徴とする化粧料。  4. It is characterized in that it contains 1 to 30% by weight of at least one selected from the group consisting of fluorinated oils (I), (II) and (III) and 5 to 95% by weight of a powder treated with a fluorinated compound. Cosmetics.
PCT/JP1997/002343 1996-07-08 1997-07-07 Cosmetic preparations containing fluorinated oils WO1998001104A1 (en)

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JP2014144935A (en) * 2013-01-30 2014-08-14 Tosoh F-Tech Inc Novel fluorine-containing alkoxysilane compound having pentaerythritol skeleton, and surface modifier and intermediate using the same

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JP2001087033A (en) * 1999-09-24 2001-04-03 Shiseido Co Ltd Bar-shaped cosmetic container
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